Fluorourethane as an additive in a photopolymer formulation

ABSTRACT

The invention relates to a photopolymer formulation comprising matrix polymers, writing monomers, and photoinitiators, to the use of the photopolymer formulation for producing optical elements, in particular for producing holographic elements and images, to a method for illuminating holographic media made of the photopolymer formulation, and to special fluorourethanes.

The invention relates to a photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, the use of the photopolymer formulation for the production of optical elements, in particular for the production of holographic elements and images, a method for the exposure of holographic media comprising the photopolymer formulation and special fluorourethanes.

WO 2008/125229 A1 describes photopolymer formulations of the type mentioned at the outset. These comprise polyurethane-based matrix polymers, acrylate-based writing monomers and photoinitiators. In the cured state, the writing monomers and the photoinitiators are embedded with spatial distribution in the polyurethane matrix. It is also known from the WO document that dibutyl phthalate, a conventional plasticizer for industrial plastics, can be added to the photopolymer formulation.

For the uses of photopolymer formulations in the fields of use described below, the refractive index modulation Δn produced by the holographic exposure in the photopolymer plays the decisive role. During the holographic exposure, the interference field of signal light beam and reference light beam (in the simplest case, that of two plane waves) is mapped into a refractive index grating by the local photopolymerization of, for example, highly refracting acrylates at sites of high intensity in the interference field. The refractive index grating in the photopolymer (the hologram) contains all information of the signal light beam. By illuminating the hologram only with the reference light beam, the signal can then be reconstructed. The strength of the signal thus reconstructed in relation to the strength of the incident reference light is referred to as diffraction efficiency, DE below. In the simplest case of a hologram which forms from the superposition of two plane waves, the DE is obtained from the quotient of the intensity of the light diffracted on reconstruction and the sum of the intensities of the incident reference light and diffracted light. The higher the DE, the more efficient is a hologram with respect to the necessary quantity of reference light which is required for making the signal visible with a fixed brightness. Highly refracting acrylates are capable of producing refractive index gratings having a high amplitude between regions having the lowest refractive index and regions having the highest refractive index and hence permitting holograms with high DE and high Δn in photopolymer formulations. It should be noted that the DE is dependent on the product of Δn and the photopolymer layer thickness d. The greater the product, the greater is the possible DE (for reflection holograms). The width of the angular range in which the hologram is visible (reconstructed), for example on monochromatic illumination, depends only on the layer thickness d. On illumination of the hologram with, for example, white light, the width of the spectral range which can contribute to the reconstruction of the hologram likewise depends only on the layer thickness d. The smaller d in this case, the greater are the respective acceptance widths. If it is therefore intended to produce bright and readily visible holograms, a high Δn·d and a small thickness d are desirable, in particular so that DE will be as large as possible. This means that the higher Δn, the more latitude is achieved for producing bright holograms by adaptation of d and without loss of DE. The optimization of Δn is therefore of outstanding importance in the optimization of photopolymer formulations (P. Hariharan, Optical Holography, 2nd Edition, Cambridge University Press, 1996.).

It was an object of the present invention to provide a photopolymer formulation which permits the production of holograms having greater brightness in comparison with the known formulations.

This object is achieved in the case of the photopolymer formulation according to the invention by virtue of the fact that it comprises fluorourethanes as plasticizers. Thus, it was found that the addition of fluorourethanes to the known photopolymer formulations leads to high Δn values in the holograms produced therefrom. As result, this means that the holograms produced from the formulation according to the invention have a higher brightness compared with the known holograms.

The fluorourethanes are preferably compounds which have a structural element of the general formula (I)

and are substituted by at least one fluorine atom.

It is more preferable if the fluorourethanes have the general formula (II)

in which n is ≧1 and n is ≦8 and R¹, R², R³ are hydrogen and/or, independently of one another, linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms, at least one of the radicals R¹, R², R³ being substituted by at least one fluorine atom. It is particularly preferable here if R¹ is an organic radical having at least one fluorine atom.

According to a further embodiment, R¹ may comprise 1-20 CF₂ groups and/or one or more CF₃ groups, particularly preferably 1-15 CF₂ groups and/or one or more CF₃ groups, particularly preferably 1-10 CF₂ groups and/or one or more CF₃ groups, very particularly preferably 1-8 CF₂ groups and/or one or more CF₃ groups, R² may comprise a C1-C20 alkyl radical, preferably a C1-C15 alkyl radical, particularly preferably a C1-C10 alkyl radical, or hydrogen, and/or R³ may comprise a C1-C20 alkyl radical, preferably a C1-C15 alkyl radical, particularly preferably a C1-C10 alkyl radical, or hydrogen.

It is particularly preferable if the fluorourethanes have uretdione, isocyanurate, biuret, allophanate, polyurea, oxadiazadione and/or iminooxadiazinedione structural elements and/or mixtures of these structural elements.

The fluorourethanes may have in particular a refractive index n_(D) ²⁰ of ≦1.4600, preferably of ≦1.4500, particularly preferably of ≦1.4400 and especially preferably of ≦1.4300.

The fluorourethanes may have a fluorine content of 10-80% by weight of fluorine, preferably of 12.5-75% by weight of fluorine, particularly preferably of 15-70% by weight of fluorine and especially preferably 17.5-65% by weight of fluorine.

The fluorourethanes of the formula (III) are obtainable by reacting isocyanates of the formula R[NCO]_(n) with fluorinated alcohols in a stoichiometric ratio to one another with urethane formation.

Preferred isocyanates of the formula R[NCO]_(n) are methyl isocyanate, ethyl isocyanate, the isomeric propyl isocyanates, the isomeric butyl isocyanates, the isomeric pentyl isocyanates, the isomeric hexyl isocyanates, the isomeric heptyl isocyanates, the isomeric octyl isocyanates, the isomeric nonyl isocyanates, the isomeric decyl isocyanates, stearyl isocyanate, cyclopropyl isocyanate, cyclobutyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, cycloheptyl isocyanate, 2-methylpentane 1,5-diisocyanate (MPDI), dodecamethylene diisocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane (TIN), 6-diisocyanatohexane (HDI, Desmodur H), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI, Desmodur I), 2,4,4-trimethylhexane 1,6-diisocyanate (TMDI), dicyclohexylmethane diisocyanate (Desmodur W), hexahydrotolylene diisocyanate (H6TDI), bis(4-isocyanatocyclohexyl)methane (H12-MDI), 1,3-bis(isocyanatomethyl)cyclohexane, Desmodur LD, Desmodur N 100, Desmodur N3200, Desmodur N3300, Desmodur N3350, Desmodur N3368, Desmodur N3375, Desmodur N3390, Desmodur N3400, Desmodur N3600, Desmodur N3790, Desmodur N3800, Desmodur N3900, Desmodur N50, Desmodur N75, Desmodur NZ1, Desmodur PL340, Desmodur PL350, Desmodur PM76, Desmodur BL3175, Desmodur BL3272, Desmodur BL3370, Desmodur BL3475, Desmodur BL4265, Desmodur BL5375, Desmodur BLXP2677, Desmodur DA-L, Desmodur DN, Desmodur E 305, Desmodur E3265, Desmodur E3370, Baymicron OXA, Desmodur VP LS 2078/2, Desmodur VP LS 2114/1, Desmodur VP LS 2257, Desmodur VP LS 2352/1, Desmodur VP LS 2371, Desmodur VP LS 2376/1, Desmodur XP 2406, Desmodur XP 2489, Desmodur XP 2565, Desmodur XP 2580, Desmodur XP 2599, Desmodur XP 2617, Desmodur XP 2626, Desmodur XP 2675, Desmodur XP 2679, Desmodur XP 2714, Desmodur XP 2730, Desmodur XP 2731, Desmodur XP 2742, Desmodur XP 2748, Desmodur Z 4470 or mixtures thereof.

Particularly preferred isocyanates of the formula R[NCO]_(n) are isomeric propyl isocyanates, the isomeric butyl isocyanates, the isomeric pentyl isocyanates, the isomeric hexyl isocyanates, the isomeric heptyl isocyanates, the isomeric octyl isocyanates, the isomeric nonyl isocyanates, the isomeric decyl isocyanates, stearyl isocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane (TIN), 6-diisocyanatohexane (HDI, Desmodur H), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI, Desmodur I), 2,4,4-trimethylhexane 1,6-diisocyanate (TMDI), dicyclohexylmethane diisocyanate (Desmodur W), hexahydrotolylene diisocyanate (H6TDI), 1,3-bis(isocyanatomethyl)-cyclohexane, Desmodur LD, Desmodur N3400, Desmodur N3600, Baymicron OXA or mixtures thereof.

Very particularly preferred isocyanates of the formula R[NCO]_(n) are isopropyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, n-octyl isocyanate, n-decyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate, 1,8-diisocyanato-4-(isocyanatomethyl)octane (TIN), 6-diisocyanatohexane (HDI, Desmodur H), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI, Desmodur I), 2,4,4-trimethylhexane 1,6-diisocyanate (TMDI), dicyclohexylmethane diisocyanate (Desmodur W), hexahydrotolylene diisocyanate (H6TDI), 1,3-bis(isocyanatomethyl)cyclohexane, Desmodur LD, Desmodur N3400, Desmodur N3600, Desmodur N3900, Baymicron OXA or mixtures thereof.

The possible choice of the fluorinated alcohols is broad, and it is preferable to use primary or secondary, mono-, di- or trifunctional alcohols having a fluorine content of 30% to 82% of fluorine, particularly preferably having a fluorine content of 40% to 80% of fluorine and especially preferably having a fluorine content of 49% to 75% of fluorine.

The reaction of isocyanates with alcohols of the type mentioned in each case above for the preparation of the fluorourethanes is a urethanization. The reaction can be effected with the aid of the catalysts known for accelerating isocyanate addition reactions, such as, for example, tertiary amines, tin, zinc, iron or bismuth compounds, in particular triethylamine, 1,4-diazabicyclo[2.2.2]octane, bismuth octoate, zinc octoate or dibutyltin dilaurate, which can be initially introduced or metered in later.

The fluorourethanes may have a content of isocyanate groups (M=42 g/mol) or free isocyanate radical monomers of less than 0.5% by weight, preferably of less than 0.2% by weight, particularly preferably of less than 0.1% by weight.

Furthermore, the fluorourethanes may have contents of unreacted hydroxy-functional compounds of less than 1% by weight, preferably of less than 0.5% by weight and particularly preferably of less than 0.2% by weight.

The fluorourethanes may have a fluorine content of 10-80% by weight of fluorine, preferably of 12.5-75% by weight of fluorine, particularly preferably of 15-70% by weight of fluorine and especially preferably of 17.5-65% by weight of fluorine.

The fluorourethanes have a refractive index n_(D) ²⁰ of ≦1.4600, preferably of ≦1.4500, particularly preferably of ≦1.4400 and especially preferably of ≦1.4300.

In the preparation of the fluorourethanes, the isocyanates and the alcohols may each be dissolved in a nonreactive solvent, for example an aromatic or aliphatic hydrocarbon or an aromatic or aliphatic halogenated hydrocarbon or a coating solvent, such as, for example, ethyl acetate or butyl acetate or acetone or butanone or an ether, such as tetrahydrofuran or tert-butyl methyl ether, or a dipolar aprotic solvent, such as dimethyl sulphoxide or N-methylpyrrolidone or N-ethylpyrrolidone, and may be initially introduced or metered in a manner familiar to the person skilled in the art.

After the end of the reaction, the unreactive solvents can be removed from the mixture under atmospheric pressure or under reduced pressure and the end point determined by determining the solids content. The solids contents are typically in a range from 99.999 to 95.0% by weight, preferably from 99.998 to 98.0% by weight, based on the fluorourethane.

The matrix polymers may be in particular polyurethanes. Preferably, the polyurethanes are obtainable by reacting an isocyanate component a) with an isocyanate-reactive component b).

The isocyanate component a) preferably comprises polyisocyanates. Polyisocyanates which may be used are all compounds well known per se to the person skilled in the art or mixtures thereof which have on average two or more NCO functions per molecule. These may have an aromatic, araliphatic, aliphatic or cycloaliphatic basis. In minor amounts, it is also possible concomitantly to use monoisocyanates and/or poly isocyanates containing unsaturated groups.

For example, butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis(4,4′-isocyanatocyclohexyl)methanes and mixtures thereof having any desired isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate and/or triphenylmethane 4,4′,4″-triisocyanate are suitable.

The use of derivatives of monomeric di- or triisocyanates having urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and/or iminooxadiazinedione structures is also possible.

The use of polyisocyanates based on aliphatic and/or cycloaliphatic di- or triisocyanates is preferred.

Particularly preferably, the polyisocyanates of component a) are dimerized or oligomerized aliphatic and/or cycloaliphatic di- or triisocyanates.

Isocyanurates, uretdiones and/or iminooxadiazinediones based on HDI, 1,8-diisocyanato-4-(isocyanatomethyl)octane or mixtures thereof are very particularly preferred.

It is also possible to use NCO-functional prepolymers having urethane, allophanate, biuret and/or amide groups as component a). Prepolymers of component a) are obtained in a manner well known per se to the person skilled in the art by reacting monomeric, oligomeric or polyisocyanates a1) with isocyanate-reactive compounds a2) in suitable stoichiometry with optional use of catalysts and solvents.

Suitable polyisocyanates a1) are all aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanates known per se to the person skilled in the art, it being unimportant whether these were obtained by means of phosgenation or by phosgene-free processes. In addition, it is also possible to use the higher molecular weight secondary products of monomeric di- and/or triisocyanates having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazinedione structure, in each case individually or as any desired mixtures with one another, which secondary products are well known per se to the person skilled in the art.

Examples of suitable monomeric di- or triisocyanates which can be used as component a1) are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl-hexamethylene diisocyanate (TMDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, isocyanato-methyl-1,8-octane diisocyanate (TIN), 2,4- and/or 2,6-toluene diisocyanate.

OH-functional compounds are preferably used as isocyanate-reactive compounds a2) for the synthesis of the prepolymers. These are analogous to the OH-functional compounds as described below for the component b).

Also possible is the use of amines for the prepolymer preparation. For example ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, diaminocyclohexane, diaminobenzene, diaminobisphenyl, difunctional polyamines, such as, for example, the Jeffamine®, amine-terminated polymers having number average molar masses of up to 10 000 g/mol or any desired mixtures thereof with one another, are suitable.

For the preparation of prepolymers containing biuret groups, isocyanate is reacted in excess with amine, a biuret group forming in the process. Suitable amines in this case for the reaction with the di-, tri- and polyisocyanates mentioned are all oligomeric or polymeric, primary or secondary, difunctional amines of the abovementioned type.

Preferred prepolymers are urethanes, allophanates or biurets obtained from aliphatic isocyanate-functional compounds and oligomeric or polymeric isocyanate-reactive compounds having number average molar masses of 200 to 10 000 g/mol; urethanes, allophanates or biurets obtained from aliphatic isocyanate-functional compounds and oligomeric or polymeric polyols or polyamines having number average molar masses of 500 to 8500 g/mol are particularly preferred and allophanates obtained from HDI or TMDI and difunctional polyether polyols having number average molar masses of 1000 to 8200 g/mol are very particularly preferred.

The prepolymers described above preferably have residual contents of free monomeric isocyanate of less than 1% by weight, particularly preferably less than 0.5% by weight, very particularly preferably less than 0.2% by weight.

Of course, the isocyanate component may contain proportionately further isocyanate components in addition to the prepolymers described. Aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates are suitable for this purpose. It is also possible to use mixtures of such di-, tri- or polyisocyanates. Examples of suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4-(isocyanatomethyl)octane, 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate (TMDI), the isomeric bis(4,4′-isocyanatocyclohexyl)methanes and mixtures thereof having any desired isomer content, isocyanatomethyl-1,8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate, triphenyl-methane 4,4′,4″-triisocyanate or derivatives thereof having a urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione or iminooxadiazinedione structure and mixtures thereof. Polyisocyanates based on oligomerized and/or derivatized diisocyanates which were freed from excess diisocyanate by suitable methods are preferred, in particular those of hexamethylene diisocyanate. The oligomeric isocyanurates, uretdiones and iminooxadiazinediones of HDI and mixtures thereof are particularly preferred.

It is optionally also possible for the isocyanate component a) proportionately to contain isocyanates which are partly reacted with isocyanate-reactive ethylenically unsaturated compounds. α,β-unsaturated carboxylic acid derivatives, such as acrylates, methacrylates, maleates, fumarates, maleimides, acrylamides, and vinyl ethers, propenyl ethers, allyl ethers and compounds which contain dicyclopentadienyl units and have at least one group reactive towards isocyanates are preferably used here as isocyanate-reactive ethylenically unsaturated compounds; these are particularly preferably acrylates and methacrylates having at least one isocyanate-reactive group. For example, compounds such as 2-hydroxyethyl (meth)acrylate, polyethylene oxide mono(meth)acrylates, polypropylene oxide mono(meth)acrylates, polyalkylene oxide mono(meth)acrylates, poly(c-caprolactone) mono(meth)-acrylates, such as, for example, Tone® M100 (Dow, USA), 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl (meth)acrylate, the hydroxy-functional mono-, di- or tetra(meth)acrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or industrial mixtures thereof are suitable as hydroxy-functional acrylates or methacrylates. In addition, isocyanate-reactive oligomeric or polymeric unsaturated compounds containing acrylate and/or methacrylate groups, alone or in combination with the abovementioned monomeric compounds, are suitable. The proportion of isocyanates which are partly reacted with isocyanate-reactive ethylenically unsaturated compounds, based on the isocyanate component a), is 0 to 99%, preferably 0 to 50%, particularly preferably 0 to 25% and very particularly preferably 0 to 15%.

It is optionally also possible for the abovementioned isocyanate component a) completely or proportionately to contain isocyanates which are completely or partly reacted with blocking agents known to the person skilled in the art from coating technology. The following may be mentioned as an example of blocking agents: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as, for example, butanone oxime, diisopropylamine, 1,2,4-triazole, dimethyl-1,2,4-triazole, imidazole, diethyl malonate, ethyl acetoacetate, acetone oxime, 3,5-dimethylpyrazole, ε-caprolactam, N-tert-butylbenzylamine, cyclopentanone carboxyethyl ester or any desired mixtures of these blocking agents.

In principle, all polyfunctional, isocyanate-reactive compounds which have on average at least 1.5 isocyanate-reactive groups per molecule can be used as component b).

Isocyanate-reactive groups in the context of the present invention are preferably hydroxy, amino or thio groups; hydroxy compounds are particularly preferred.

Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester-, polyether-, polycarbonate-, poly(meth)acrylate- and/or polyurethanepolyols.

Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols, as can be obtained in a known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality of ≧2.

Examples of such di- or polycarboxylic acids or anhydrides are succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic or trimellitic acid and acid anhydrides, such as o-phthalic, trimellitic or succinic anhydride, or any desired mixtures thereof with one another.

Examples of such suitable alcohols are ethanediol, di-, tri- and tetraethylene glycol, 1,2-propanediol, di-, tri- and tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, trimethylolpropane, glycerol or any desired mixtures thereof with one another.

The polyester polyols may also be based on natural raw materials, such as castor oil. It is also possible for the polyester polyols to be based on homo- or copolymers of lactones, as can preferably be obtained by an addition reaction of lactones or lactone mixtures, such as butyrolactone, ε-caprolactone and/or methyl-ε-caprolactone, with hydroxy-functional compounds, such as polyhydric alcohols having an OH functionality of ≧2, for example of the abovementioned type.

Such polyester polyols preferably have number average molar masses of 400 to 4000 g/mol, particularly preferably of 500 to 2000 g/mol. Their OH functionality is preferably 1.5 to 3.5, particularly preferably 1.8 to 3.0.

Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.

Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.

Suitable diols or mixtures comprise the polyhydric alcohols known per se in relation to the polyester segments and having an OH functionality of ≧2, preferably 1,4-butanediol, 1,6-hexanediol and/or 3-methylpentanediol, or polyester polyols can be converted into polycarbonate polyols.

Such polycarbonatepolyols preferably have number average molar masses of 400 to 4000 g/mol, particularly preferably of 500 to 2000 g/mol. The OH functionality of these polyols is preferably 1.8 to 3.2, particularly preferably 1.9 to 3.0.

Suitable polyether polyols are optionally polyadducts of cyclic ethers with OH- or NH-functional starter molecules, which polyadducts have a block structure.

Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any desired mixtures thereof.

The polyhydric alcohols mentioned in relation to the polyester polyols and having an OH functionality of ≧2 and primary or secondary amines and amino alcohols may be used as starters.

Preferred polyether polyols are those of the abovementioned type, exclusively based on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides, the proportion of 1-alkylene oxide not being higher than 80% by weight. In addition, poly(trimethylene oxides) and mixtures of the polyols mentioned as being preferred are preferred. Propylene oxide homopolymers and random or block copolymers which have oxyethylene, oxypropylene and/or oxybutylene units are particularly preferred, the proportion of the oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, accounting for at least 20% by weight, preferably at least 45% by weight. Here, oxypropylene and oxybutylene comprise all respective linear and branched C₃ and C₄ isomers.

Such polyether polyols preferably have number average molar masses of 250 to 10 000 g/mol, particularly preferably of 500 to 8500 g/mol and very particularly preferably of 600 to 4500 g/mol. The OH functionality is preferably 1.5 to 4.0, particularly preferably 1.8 to 3.1.

In addition, aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols having a low molecular weight, i.e. having molecular weights of less than 500 g/mol, and having a short chain, i.e. containing 2 to 20 carbon atoms, are also suitable as constituents of component b), as polyfunctional, isocyanate-reactive compounds.

These may be, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomers of diethyloctanediols, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis(4-hydroxycyclohexyl)propane), 2,2-dimethyl-3-hydroxypropionic acid (2,2-dimethyl-3-hydroxypropyl ester). Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol. Suitable high-functional alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.

One or more photoinitiators are used as component c). These are usually initiators which can be activated by actinic radiation and initiate a polymerization of the corresponding polymerizable groups. Photoinitiators are commercially distributed compounds known per se, the distinction being made between monomolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, these initiators are used for free radical, anionic (or), cationic (or mixed) forms of the abovementioned polymerizations.

(Type I) systems for free radical photopolymerization are, for example, aromatic ketone compounds, e.g. benzophenones, in combination with tertiary amines, alkylbenzophenones, 4,4′-bis(dimethylamino)benzophenone (Michlers ketone), anthrone and halogenated benzophenones or mixtures of said types. Further suitable are (type II) initiators, such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, e.g. 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylophosphine oxides, phenylglyoxylic esters, camphorquinone, alpha-aminoalkylphenones, alpha-,alpha-dialkoxyacetophenones, 1-[4-(phenylthio)phenyl]octane-1,2-dione 2-(O-benzoyloxime), differently substituted hexarylbisimidazoles (HABI) with suitable coinitiators, such as, for example, mercaptobenzoxazole and alpha-hydroxyalkylphenones. The photoinitiator systems described in EP-A 0223587 and consisting of a mixture of an ammonium arylborate and one or more dyes can also be used as a photoinitiator. Suitable ammonium arylborates are, for example, tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylbutylborate, tetramethylammonium triphenylbenzylborate, tetra(n-hexyl)ammonium (sec-butyl)triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate, tetrabutylammonium tris-(4-tert-butyl)phenylbutylborate, tetrabutylammonium tris-(3-fluorophenyl)hexylborate and tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexylborate. Suitable dyes are, for example, new methylene blue, thionine, basic yellow, pinacynol chloride, rhodamine 6G, gallocyanine, ethyl violet, Victoria blue R, Celestine blue, quinaldine red, crystal violet, brilliant green, astrazone orange G, darrow red, pyronine Y, basic red 29, pyrillium I, safranin 0, cyanine and methylene blue, azure A (Cunningham et al., RadTech'98 North America UV/EB Conference Proceedings, Chicago, Apr. 19-22, 1998).

The photoinitiators used for the anionic polymerization are as a rule (type I) systems and are derived from transition metal complexes of the first series. Mention should be made here of chromium salts, such as, for example, trans-Cr(NH₃)₂(NCS)₄— (Kutal et al, Macromolecules 1991, 24, 6872), or ferrocenyl compounds (Yamaguchi et al. Macromolecules 2000, 33, 1152). A further possibility of anionic polymerization consists in the use of dyes, such as crystal violet, leuconitrile or malachite green leuconitrile, which can polymerise cyanoacrylates by photolytic decomposition (Neckers et al. Macromolecules 2000, 33, 7761). However, the chromophore is incorporated into the polymer thereby so that the resulting polymers are coloured throughout.

The photoinitiators used for the cationic polymerization substantially comprise three classes: aryldiazonium salts, onium salts (here especially: iodonium, sulphonium and selenonium salts) and organometallic compounds. On irradiation both in the presence and in the absence of a hydrogen donor, phenyldiazonium salts can produce a cation which initiates the polymerization. The efficiency of the total system is determined by the nature of the counterion used for the diazonium compound. The not very reactive but very expensive SbF₆—, AsF₆— or PF₆— is preferred here. These compounds are as a rule not very suitable for use in the coating of thin films since the surface quality is reduced (pinholes) by the nitrogen liberated after the exposure (Li et al., Polymeric Materials Science and Engineering, 2001, 84, 139). Very widely used and also commercially available in many forms are onium salts, especially sulphonium and iodonium salts. The photochemistry of these compounds has been investigated for a long time. After excitation, the iodonium salts decompose initially homolytically and thus produce a free radical and a radical anion which is stabilized by H abstraction and liberates a proton and then initiates the cation polymerization (Dektar et al. J. Org. Chem. 1990, 55, 639; J. Org. Chem., 1991, 56. 1838). This mechanism permits the use of iodonium salts also for free radical photopolymerization. Once again, the choice of the counterion is of considerable importance here; SbF₆ ⁻, AsF₆ ⁻ or PF₆ ⁻ is likewise preferred. Otherwise, the choice of the substitution of the aromatic is entirely free in this structure class and is determined substantially by the availability of suitable starting building blocks for the synthesis. The sulphonium salts are compounds which decompose according to Norrish(II) (Crivello et al., Macromolecules, 2000, 33, 825). In the case of the sulphonium salts, too, the choice of the counterion is of critical importance, which manifests itself substantially in the curing rate of the polymers. The best results are obtained as a rule with SbF₆ salts. Since the self-absorption of iodonium and sulphonium salts is at <300 nm, these compounds must be appropriately sensitized for photopolymerization with near UV or short-wave visible light. This is effected by using more highly absorbing aromatics such as, for example, anthracene and derivatives (Gu et al., Am. Chem. Soc. Polymer Preprints, 2000, 41 (2), 1266) or phenothiazine or derivatives thereof (Hua et al, Macromolecules 2001, 34, 2488-2494).

It may also be advantageous to use mixtures of these compounds. Depending on the radiation source used for the curing, type and concentration of photoinitiator must be adapted in a manner known to the person skilled in the art. Further details are described, for example, in P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pages 61-328.

Preferred photoinitiators c) are mixtures of tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinaphthylbutylborate, tetrabutylammonium tris-(4-tert-butyl)phenylbutylborate, tetrabutylammonium tris-(3-fluorophenyl)hexylborate and tetrabutylammonium tris-(3-chloro-4-methylphenyl)hexylborate with dyes, such as, for example astrazone orange G, methylene blue, new methylene blue, azure A, pyrillium 1, safranin O, cyanine, gallocyanine, brilliant green, crystal violet, ethyl violet and thionine.

As component d), very good results are obtainable with highly refracting acrylates as contrast-imparting components in photopolymer formulations, as described, for example, in U.S. Pat. No. 6,780,546.

It is therefore preferable according to the invention if, in the photopolymer formulation, the writing monomers are acrylates, particularly preferably those having a refractive index n_(D) ²⁰>1.50. Urethane acrylates are very particularly preferred; aromatic urethane acrylates having a refractive index of n_(D) ²⁰>1.50 at 589 nm, as described, for example, in WO2008/125199, are particularly preferred.

The present invention furthermore relates to media for recording visual holograms obtainable using fluorourethanes of the formula (I), the use of such media as optical elements or images or for image representation or projection and a method for recording a hologram in which such media are used.

The photopolymer formulation according to the invention may contain in particular 15 to 79, preferably 30 to 60, % by weight of matrix polymer, 5 to 50, preferably 10 to 40, % by weight of writing monomer, 1 to 10, preferably Ito 3, % by weight of photoinitiator and 5 to 50, preferably 10 to 40, % by weight of fluorourethanes and 0 to 10% by weight of further additives, the sum of the constituents being 100% by weight.

A second aspect of the invention relates to a process for the preparation of a photopolymer formulation according to the invention, in which matrix polymers, writing monomers, photoinitiators and fluorourethanes as plasticizers are mixed to give the photopolymer formulation.

A third aspect of the invention relates to a photopolymer formulation obtainable by the process.

A fourth aspect of the invention relates to a sheet, a film, a layer, a layer structure or a moulding comprising the photopolymer formulation.

Layers, layer structures and mouldings comprising the photopolymer formulations according to the invention typically have Δn values, measured by the method described in the section “Measurement of the holographic properties DE and Δn of the holographic media by means of two-beam interference in reflection arrangement”, of Δn>0.0120, preferably >0.0130, particularly preferably >0.0140, very particularly preferably >0.0150.

A fifth aspect of the invention relates to the use of the photopolymer formulation for the production of optical elements, in particular for the production of holographic elements and images.

The invention also relates to a method for exposing holographic media comprising a photopolymer formulation according to the invention, in which the writing monomers are selectively polymerized with spatial resolution by electromagnetic radiation.

After the holographic exposure, such holographic media are suitable for the production of holographic optical elements which have, for example, the function of an optical lens, a mirror, a deflection mirror, a filter, a diffuser screen, a diffraction element, a light conductor, a waveguide, a projection screen and/or a mask. In addition, it is also possible to produce holographic images or representations, such as, for example, for personal portraits, biometric representations in security documents or generally of images or image structures for advertising, security labels, trademark protection, trademark branding, labels, design elements, decorations, illustrations, multi-journey tickets, images and the like and images which can represent digital data, inter alia also in combination with the products described above.

The prior art discloses certain fluorourethanes. Thus, US 2003/105263 A1 describes fluorourethanes which are obtainable by reacting a biuret, isocyanurate, uretdione, polyurea contain the polyisocyanate with a fluorinated alcohol. WO 03/023519 A discloses fluorourethane that is obtainable by reacting a biuret-containing polyisocyanate with a fluorinated alcohol.

A further aspect of the invention relates to a fluorourethane obtainable by reacting a polyisocyanate which contains iminooxadiazinediones or oxadiazadione and has at least one free isocyanate group with an alcohol, the polyisocyanate and/or the alcohol being substituted by at least one fluorine atom.

Finally, the invention also relates to a fluorourethane according to the general formula (III)

in which m is ≧1 and m is ≦8 and R⁴, R⁵, R⁶ are hydrogen and/or, independently of one another, linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms and have iminooxadiazinedione and/or oxadiazadione structural elements, at the same time at least two of the radicals R⁴, R⁵, R⁶ being substituted by at least one fluorine atom.

EXAMPLES

The invention is explained in more detail below with reference to examples.

Unless noted otherwise, all stated percentages are based on percent by weight.

Methods of Measurement:

The stated NCO values (isocyanate contents) were determined according to DIN EN ISO 11909.

The measurement of the refractive index was effected by one of the following three methods, depending on the nature of the example compound:

Measurement of the refractive index n at a wavelength of 405 nm (Method A): the refractive index n as a function of the wavelength of the samples were obtained from the transmission and reflection spectra. For this purpose, about 100-300 nm thick films of the samples were applied by spin coating to quartz glass substrates from dilute solution in butyl acetate. The transmission and reflection spectrum of this layer packet was measured with a spectrometer from STEAG ETA-Optik, CD-Measurement System ETA-RT, and the layer thickness and the spectral curve of n were then fitted to the measured transmission and reflection spectra. This is effected using the internal software of the spectrometer and additionally requires the n data of the quartz glass substrate, which were determined beforehand in a blank measurement.

Measurement of the refractive index n_(D) ²⁰ at a wavelength of 589 nm (Method B): a sample of the example compound was introduced into an Abbe refractometer and the n_(D) ²⁰ was then measured.

Measurement of the refractive index n_(D) ²⁰ at a wavelength of 589 nm from semiconcentrated solution (Method C): a sample of the example compound was diluted 50:50 (% by weight) with N-ethylpyrrolidone and introduced into an Abbe refractometer and the n_(D) ²⁰ was then measured. The approximate refractive index of the analyte was calculated therefrom; the n_(D) ²⁰ of N-ethylpyrrolidone was 1.4658.

Measurement of the Holographic Properties DE and Δn of the Holographic Media by Means of Two-Beam Interference in Reflection Arrangement

The media produced were then tested with regard to their holographic properties by means of a measuring arrangement according to FIG. 1, as follows:

The beam of an He—Ne laser (emission wavelength 633 nm) was converted with the aid of the spatial filter (SF) and together with the collimation lens (CL) into a parallel homogeneous beam. The final cross section of the signal and reference beam are established by the iris diaphragms (I). The diameter of the iris diaphragm opening is 0.4 cm. The polarization-dependent beam splitters (PBS) split the laser beam into two coherent equally polarized beams. Via the λ/2 plates, the power of the reference beam was adjusted to 0.5 mW and the power of the signal beam to 0.65 mW. The powers were determined using the semiconductor detectors (D) with sample removed. The angle of incidence (α₀) of the reference beam is −21.8° and the angle of incidence (β₀) of the signal beam is 41.8°. The angles are measured starting from the sample normal to the beam direction. According to FIG. 1, α₀ therefore has a negative sign and β₀ a positive sign. At the location of the sample (medium), the interference field of the two overlapping beams produced a grating of light and dark strips which are perpendicular to the angle dissectors of the two beams incident on the sample (reflection hologram). The strip spacing A, also referred to as grating period, in the medium is ˜225 nm (the refractive index of the medium assumed to be ˜1.504).

FIG. 1 shows the geometry of a holographic media tester (HMT) at λ=633 nm (He—Ne laser): M=mirror, S=shutter, SF=spatial filter, CL=collimator lens, λ/2=λ/2 plate, PBS=polarization-sensitive beam splitter, D=detector, I=iris diaphragm, α₀=−21.8°, β₀=41.8° are the angles of incidence of the coherent beams, measured outside the sample (outside the medium). RD=reference direction of the turntable.

The diffraction efficiency (DE) of the media was measured using an experimental holographic setup as shown in FIG. 1.

Holograms were recorded in the medium in the following manner:

-   -   both shutters (S) are opened for the exposure time t.     -   thereafter, with closed shutters (S), the medium was allowed a         time of 5 minutes for diffusion of the as yet unpolymerized         writing monomers.

The holograms recorded were now read in the following manner. The shutter of the signal beam remained closed. The shutter of the reference beam was open. The iris diaphragm of the reference beam was closed to a diameter of <1 mm. This ensured that the beam was always completely in the previously recorded hologram for all angles of rotation (Ω) of the medium. The turntable, under computer control, now covered the angle range from Ω_(min) to Ω_(max) with an angle step width of 0.05°. Ω is measured from the sample normal to the reference direction of the turntable. The reference direction of the turntable is obtained when the angle of incidence of the reference beam and that of the signal beam have the same magnitude, i.e. α₀=−31.8° and β₀=31.8°, on recording of the hologram. Ω_(recording) is then 0°. For α₀=−21.8° and β₀=41.8°, Ω_(recording) is therefore 10°. In general, the following is true for the interference field during recording of the hologram:

α_(O)=θ₀+Ω_(recording).

θ₀ is the semiangle in the laboratory system outside the medium and the following is true for recording of the hologram:

$\theta_{0} = {\frac{\alpha_{0} - \beta_{0}}{2}.}$

In this case, θ₀ is therefore −31.8°. At each angle of rotation Ω approached, the powers of the beam transmitted in the zero order were measured by means of the corresponding detector D and the powers and the beam diffracted in the first order were measured by means of the detector D. The diffraction efficiency was obtained at each angle Ω approached as the quotient of:

$\eta = \frac{P_{D}}{P_{D} + P_{T}}$

P_(D) is the power in the detector of the diffracted beam and P_(T) is the power in the detector of the transmitted beam.

By means of the method described above, the Bragg curve (it describes the diffraction efficiency η as a function of the angle of rotation Ω□ of the recorded hologram) was measured and was stored in a computer. In addition, the intensity transmitted in the zero order was also plotted against the angle of rotation Ω and stored in a computer.

The maximum diffraction efficiency (DE=^(η)max) of the hologram, i.e. its peak value, was determined in the case of Ω_(reconstruction). It may have been necessary for this purpose to change the position of the detector of the diffracted beam in order to determine this maximum value.

The refractive index contrast Δn and the thickness d of the photopolymer layer was now determined by means of the coupled wave theory (cf. H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 page 2909-page 2947) from the measured Bragg curve and the variation of the transmitted intensity as a function of angle. It should be noted that, owing to the thickness shrinkage occurring as a result of the photopolymerization, the strip spacing Λ′ of the hologram and the orientation of the strips (slant) may deviate from the strip spacing Λ of the interference pattern and the orientation thereof. Accordingly, the angle Λ₀′ or the corresponding angle of the turntable Ω_(reconstruction) at which maximum diffraction efficiency is achieved will also deviate from 0 or from the corresponding Ω_(recording). As a result, the Bragg condition changes. This change is taken into account in the evaluation method. The evaluation method is described below:

All geometrical quantities which relate to the recorded hologram and not to the interference pattern are shown as dashed quantities.

According to Kogelnik, the following is true for the Bragg curve η(Ω) of a reflection hologram:

$\eta = \left\{ {{\begin{matrix} {\frac{1}{1 - \frac{1 - \left( {\xi/v} \right)^{2}}{\sin^{2}\left( \sqrt{\xi^{2} - v^{2}} \right)}},{{{{for}\mspace{14mu} v^{2}} - \xi^{2}} < 0}} \\ {\frac{1}{1 + \frac{1 - \left( {\xi/v} \right)^{2}}{\sinh^{2}\left( \sqrt{v^{2} - \xi^{2}} \right)}},{{{{for}\mspace{14mu} v^{2}} - \xi^{2}} \geq 0}} \end{matrix}{with}\text{:}v} = {{\frac{{\pi \cdot \Delta}\; {n \cdot d^{\prime}}}{\lambda \cdot \sqrt{{c_{s} \cdot c_{r}}}}\xi} = {{{{- \frac{d^{\prime}}{2 \cdot c_{s}}} \cdot {DP}}c_{s}} = {{{\cos \left( \vartheta^{\prime} \right)} - {{{\cos \left( \psi^{\prime} \right)} \cdot \frac{\lambda}{n \cdot \Lambda^{\prime}}}c_{r}}} = {{{\cos \left( \vartheta^{\prime} \right)}{DP}} = {{{\frac{\pi}{\Lambda^{\prime}} \cdot \left( {{2 \cdot {\cos \left( {\psi^{\prime} - \vartheta^{\prime}} \right)}} - \frac{\lambda}{n \cdot \Lambda^{\prime}}} \right)}\psi^{\prime}} = {{\frac{\beta^{\prime} + \alpha^{\prime}}{2}\Lambda^{\prime}} = \frac{\lambda}{2 \cdot n \cdot {\cos \left( {\psi^{\prime} - \alpha^{\prime}} \right)}}}}}}}}} \right.$

On reading the hologram (“reconstruction”) the following is true as described analogously above:

Θ′₀=θ₀+Ω

sin(Θ₀)=n·sin(Θ′)

Under the Bragg condition, the “dephasing” DP is 0. Accordingly:

α′₀=θ₀+Ω_(reconstruction)

sin(α′₀)=n·sin(α′)

The still unknown angle β′ can be determined from the comparison of the Bragg condition of the interference field on recording of the hologram and the Bragg condition on reading of the hologram, assuming that only thickness shrinkage takes place. The following then follows:

${\sin \left( \beta^{\prime} \right)} = {\frac{1}{n} \cdot \left\lbrack {{\sin \left( \alpha_{0} \right)} + {\sin \left( \beta_{0} \right)} - {\sin \left( {\theta_{0} + \Omega_{reconstruction}} \right)}} \right\rbrack}$

v is the grating thickness, ξ is the detuning parameter and ψ′ is the orientation (slant) of the refractive index grating which was recorded. α′ and β′ correspond to the angles α0 and β0 of the interference field on recording of the hologram, but measured in the medium and applicable to the grating of the hologram (after thickness shrinkage). n is the mean refractive index of the photopolymer and was set at 1.504. λ is the wavelength of the laser light in vacuo.

The maximum diffraction efficiency (DE=ηmax) is then obtained for ξ=0 as:

${DE} = {{\tanh^{2}(v)} = {\tanh^{2}\left( \frac{{\pi \cdot \Delta}\; {n \cdot d^{\prime}}}{\lambda \cdot \sqrt{{\cos \left( \alpha^{\prime} \right)} \cdot {\cos \left( {\alpha^{\prime} - {2\psi}} \right)}}} \right)}}$

FIG. 2 shows the measured transmitted power P_(T) (right y axis) as a solid line, plotted against the angle detuning ΔΩ, the measured diffraction efficiency η (left y axis) as solid circles, plotted against the angle detuning ΔΩ (if permitted by the finite size of the detector) and the fit of the Kogelnik theory as a dashed line (lefty axis).

The measured data of the diffraction efficiency, the theoretical Bragg curve and the transmitted intensity are, as shown in FIG. 2, plotted against the centred angle of rotation ΔΩ≡Ω_(reconstruction)−Ω=α′₀−Θ′₀, also referred to as angle detuning.

Since DE is known, the shape of the theoretical Bragg curve according to Kogelnik is determined only by the thickness d′ of the photopolymer layer. An is subsequently corrected for a given thickness d′ using DE so that measurement and theory of DE always agree. d′ is now adjusted until the angle positions of the first secondary minima of the theoretical Bragg curve agree with the angle positions of the first secondary maxima of the transmitted intensity and additionally the full width at half height (FWHM) for the theoretical Bragg curve and for the transmitted intensity agree.

Since the direction in which a reflection hologram concomitantly rotates on reconstruction by means of an Ω scan, but the detector for the diffracted light can detect only a finite angle range, the Bragg curve of broad holograms (small d′) is not completely detected in an Ω scan, but only the central region, with suitable detector positioning. The shape of the transmitted intensity which is complementary to the Bragg curve is therefore additionally used for adjusting the layer thickness d′.

FIG. 2 shows the plot of the Bragg curve η according to the coupled wave theory (dashed line), of the measured diffraction efficiency (solid circles) and of the transmitted power (black solid line) against the angle detuning ΔΩ.

For a formulation, this procedure was possibly repeated several times for different exposure times t on different media in order to determine the average energy dose of the incident laser beam at which DE reaches the saturation value during recording of the hologram. The average energy dose E is obtained from the powers of the two part-beams coordinated with the angles α₀ and β₀ (reference beam with P_(r)=0.50 mW and signal beam with P_(s)=0.63 mW), the exposure time t and the diameter of the iris diaphragm (0.4 cm), as follows:

${E\left( {{mJ}/{cm}^{2}} \right)} = \frac{2 \cdot \left\lbrack {P_{r} + P_{s}} \right\rbrack \cdot {t(s)}}{{\pi \cdot 0.4^{2}}{cm}^{2}}$

The powers of the part-beams were adjusted so that the same power density is achieved in the medium at the angles α₀ and β₀ used.

Substances Used:

Fluorlink E 10/H is a reactive additive produced by Solvay Solexis and based on a fluorinated alcohol having the average molecular weight of 750 g/mol.

CGI-909 (tetrabutylammonium tris(3-chloro-4-methylphenyl)(hexyl)borate, [1147315-11-4]) is an experimental product produced by CIBA Inc., Basle, Switzerland.

1,8-Diisocyanato-4-(isocyanatomethyl)octane (TIN) was prepared as described in EP749958.

The fluorinated alcohols and monofunctional isocyanates used were obtained from the chemical trade, and the polyisocyanates used (Desmodur H (HDI), Desmodur I (IPDI), Desmodur W, Desmodur LD, Desmodur N3400, Desmodur N3600, Desmodur N3900, Baymicron OXA) are commercial products of Bayer MaterialScience AG, Leverkusen, Germany.

2,4,4-Trimethylhexane 1,6-diisocyanate, Vestanat TMDI, is a product of Evonik Degussa GmbH, Marl, Germany.

Preparation of 2,2,2-trifluoroethyl (6-isocyanatohexyl)carbamate

684 g of hexamethylene diisocyanate (HDI) were initially introduced at 80° C. in a 1 l round-bottomed flask and 0.002 g of isophthaloyl dichloride was added. 54.4 g of trifluoroethanol were slowly added dropwise and stirring was effected until the NCO value was 43.2% by weight. The mixture was separated by distillation on a thin-film evaporator and 47 g (=47% of theory) of the title compound having an NCO content of 22.7% by weight were obtained.

Preparation of 2,2,3,3,4,4,5,5-octafluoropentyl (6-isocyanatohexyl)carbamate

399 g of hexamethylene diisocyanate (HDI) were initially introduced at 80° C. in a 1 l round-bottomed flask and 0.002 g of isophthaloyl dichloride was added. 73.4 g of 2,2,3,3,4,4,5,5-octafluoropentanol were slowly added dropwise and stirring was effected until the NCO value was 39.4% by weight. The mixture was separated by distillation on a thin-film evaporator and 40 g (=40% of theory) of the title compound having an NCO content of 12.4% by weight were obtained.

Example 1 Bis(2,2,2-trifluoroethyl)hexane-1,6-diyl biscarbamate 0.07 g of Desmorapid Z and 64.4 g of 6-diisocyanatohexane (HDI) were initially introduced into a 500 ml round-bottomed flask and heated to 60° C. Thereafter, 81.5 g of trifluoroethanol were added dropwise and the mixture was further kept at 60° C. until the isocyanate content had fallen below 0.1%. Cooling was then effected. The product was obtained as a colourless solid.

The examples described below in Table 1 were prepared in the manner described in Example 1, in the stated compositions.

TABLE 1 Preparation and characterization of Examples 2-224 Ex- Refractive am- Isocyanate and Alcohol and Catalyst and Temp index ple Name amount amount amount [° C.] Description (Method) 2 2,2,2-Trifluoroethyl butylcarbamate n-Butyl isocyanate Trifluoroethanol Desmorapid Z 60° C. colourless 1.3900 (B) 498 g 502 g 0.50 g liquid 3 2,2,2-Trifluoroethyl Isopropyl Trifluoroethanol Desmorapid Z 60° C. colourless 1.3834 (C) isopropylcarbamate isocyanate 27.0 g 0.02 g solid 22.9 g 4 2,2,2-Trifluoroethyl hexylcarbamate n-Hexyl isocyanate Trifluoroethanol Desmorapid Z 60° C. colourless 1.3984 (B) 55.9 g 44.0 g 0.05 g liquid 5 1,1,1,3,3,3-Hexafluoropropan-2-yl n-Hexyl isocyanate Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.3711 (B) hexylcarbamate 10.8 g 14.2 g 0.01 g liquid 6 2,2,3,3-Tetrafluoropropyl n-Hexyl isocyanate 2,2,3,3-Tetra- Desmorapid Z 60° C. colourless 1.4020 (B) hexylcarbamate 12.3 g fluoropropan-1-ol 0.01 g liquid 12.7 g 7 1,1,1,3,3,3-Hexafluoropropan-2-yl n-Butyl isocyanate Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.3650 (C) butylcarbamate 9.3 g 15.7 g 0.01 g solid 8 2,2,3,3-Tetrafluoropropyl n-Butyl isocyanate 2,2,3,3-Tetra- Desmorapid Z 60° C. colourless 1.4100 (A) butylcarbamate 10.7 g fluoropropan-1-ol 0.01 g liquid 14.3 g 9 1,1,1,3,3,3-Hexafluoropropan-2-yl n-Octyl isocyanate Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.3910 (A) octylcarbamate 9.6 g 10.4 g 0.01 g solid 10 2,2,2-Trifluoroethyl octylcarbamate n-Octyl isocyanate Trifluoroethanol Desmorapid Z 60° C. colourless 1.4083 (B) 12.2 g 7.8 g 0.01 g liquid 11 1,1,1,3,3,3-Hexafluoropropan-2-yl n-Decyl isocyanate Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.4022 (C) octylcarbamate 10.4 g 9.6 g 0.01 g solid 12 2,2,2-Trifluoroethyl decylcarbamate n-Decyl isocyanate Trifluoroethanol Desmorapid Z 60° C. colourless 1.4178 (C) 12.9 g 7.1 g 0.01 g solid 13 Bis(1,1,1,3,3,3-hexafluoropropan-2- 6-Diisocyanato- Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.4300 (A) yl) hexane-1,6-diylbiscarbamate hexane (HDI) 13.3 g 0.01 g solid 6.7 g 14 Bis(1,1,1,3,3,3-hexafluoropropan-2- 2,4,4-Trimethyl- Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.4270 (A) yl)-(2,2,4-trimethylhexane-1,6-diyl) hexane 1,6- 80.0 g 0.07 g liquid biscarbamate diisocyanate (TMDI) 50.0 g 15 Bis(2,2,2-trifluoroethyl)-(2,2,4- 2,4,4-Trimethyl- Trifluoroethanol Desmorapid Z 60° C. colourless 1.4800 (A) trimethylhexane-1,6-diyl) hexane 1,6- 463 g 0.48 G liquid biscarbamate diisocyanate (TMDI) 496 g 16 1,1,1,3,3,3-Hexafluoropropan-2-yl Stearyl isocyanate Hexafluoro-2-propanol Desmorapid Z 60° C. colourless n.d. stearylcarbamate 12.7 g 7.27 g 0.01 g solid 17 2,2,2-Trifluoroethyl stearylcarbamate Stearyl isocyanate Trifluoroethanol Desmorapid Z 60° C. colourless n.d. 14.9 g 5.1 g 0.01 g solid 18 Bis(1,1,1,3,3,3-hexafluoropropan-2- 1,8-Diisocyanato-4- Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.3920 (B) yl)-{4-[({[(1,1,1,3,3,3- (isocyanatomethyl)- 6.66 g 0.01 g solid hexafluoropropan-2- octane (TIN) yl)oxy]carbonyl}- 3.33 g amino)methyl]octane-1,8-diyl} biscarbamate 19 Bis(2,2,2-trifluoroethyl)-[4-({[(2,2,2- 1,8-Diisocyanato-4- Trifluoroethanol Desmorapid Z 60° C. colourless 1.4213 (B) trifluoroethoxy)carbonyl]amino}- (isocyanatomethyl)- 272 g 0.48 g liquid methyl)octane-1,8-diyl] biscarbamate octane (TIN) 228 g 20 2,2,3,3,4,4,4-Heptafluorobutyl n-Butyl isocyanate 2,2,3,3,4,4,4-Hepta- Desmorapid Z 60° C. colourless 1.3625 (B) butylcarbamate 24.8 g fluorobutanol 0.04 g solid 50.1 g 21 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 60° C. colourless 1.3555 (B) Hexadecafluorononyl butylcarbamate 186 g 8,8,9,9-Hexadeca- 0.50 g liquid fluorononanol 813 g 22 Bis(2,2,3,3,4,4,4-heptafluorobutyl)- 2,4,4- 2,2,3,3,4,4,4-Hepta- Desmorapid Z 60° C. colourless 1.3887 (B) (2,2,4-trimethylhexane-1,6-diyl) Trimethylhexane fluorobutanol 0.01 g liquid biscarbamate 1,6-diisocyanate 13.1 g (TMDI) 6.88 g 23 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- 2,4,4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 60° C. colourless 1.3733 (B) hexadecafluorononyl)-(2,2,4- Trimethylhexane 8,8,9,9- 0.01 g liquid trimethylhexane-1,6-diyl) 1,6-diisocyanate Hexadecafluoro- biscarbamate (TMDI) nonanol 3.91 g 16.1 g 24 Bis(2,2,3,3,4,4,4-heptafluorobutyl)- 1,8-Diisocyanato-4- 2,2,3,3,4,4,4-Hepta- Desmorapid Z 60° C. colourless 1.3876 (B) [4-({[(2,2,3,3,4,4,4- (isocyanato- fluorobutanol 0.01 g oil heptafluorobutoxy)- methyl)octane (TIN) 14.1 g carbonyl]amino}methyl)octane- 5.91 g 1,8-diyl] biscarbamate 25 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 60° C. colourless 1.3890 (C) hexadecafluorononyl)-{4- (isocyanatomethyl)- 8,8,9,9- 0.01 g oil [({[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- octane (TIN) Hexadecafluoro- hexadecafluorononyl)oxy]carbonyl}- 3.25 g nonanol amino)methyl]octane-1,8-diyl} 16.7 g biscarbamate 26 2,2,3,3,4,4,5,5,5-Nonafluoropentyl n-Butyl isocyanate 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3580 (B) butylcarbamate 4.25 g Nonafluoropentan-1-ol 0.02 g liquid 10.7 g 27 Bis(2,2,3,3,4,4,5,5,5- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3786 (B) nonafluoropentyl)-{4- (isocyanatomethyl)- Nonafluoropentan-1-ol 0.02 g oil [({[(2,2,3,3,4,4,5,5,5-nona- octane (TIN) 11.2 g fluoropentyl)oxy]carbonyl}- 3.77 g amino)methyl]octane-1,8-diyl} biscarbamate 28 Bis(2,2,3,3,4,4,5,5,5- 2,4,4- 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3820 (B) nonafluoropentyl)-(2,2,4- Trimethylhexane Nonafluoropentan-1-ol 0.02 g liquid trimethylhexane-1,6-diyl) 1,6-diisocyanate 10.6 g biscarbamate (TMDI) 4.43 g 29 Bis(2,2,3,3,4,4,5,5,5- 6-Diisocyanato- 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3876 (C) nonafluoropentyl) hexane-1,6- hexane (HDI) Nonafluoropentan-1-ol 0.02 g solid diylbiscarbamate 3.77 g 11.2 g 30 Bis(2,2,3,3,4,4,5,5,5- Dicyclohexyl- 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4124 (C) nonafluoropentyl) methane diiso- Nonafluoropentan-1-ol 0.02 g solid (methanediyldicyclohexane-4,1-diyl) cyanate (Desmodur 9.83 g biscarbamate W) 5.15 g 31 2,2,3,3,4,4,5,5,5-Nonafluoropentyl- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3984 (C) {[1,3,3-trimethyl-5- trimethyl-5- Nonafluoropentan-1-ol 0.02 g solid ({[(2,2,3,3,4,4,5,5,5- isocyanatomethyl- 10.4 g nonafluoropentyl)oxy]carbonyl}- cyclohexane (IPDI) amino)cyclohexyl]methyl}carbamate 4.61 g 32 2,2,3,3,4,4,5,5,5-Nonafluoropentyl n-Hexyl isocyanate 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3690 (B) hexylcarbamate 5.05 g Nonafluoropentan-1-ol 0.02 g liquid 9.94 g 33 Bis(2,2,3,3,4,4,5,5,5- Hexahydrotolylene 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3940 (C) nonafluoropentyl)-(4- diisocyanate Nonafluoropentan-1-ol 0.02 g oil methylcyclohexane-1,3-diyl) (H6TDI) 11.0 g biscarbamate 3.97 g 34 2,2,3,3,4,4,5,5,5-Nonafluoropentyl Isopropyl 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3497 (B) propan-2-yl carbamate isocyanate Nonafluoropentan-1-ol 0.02 g liquid 3.81 g 11.2 g 35 2,2,3,3,4,4,5,5,5-Nonafluoropentyl Cyclohexyl 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.3952 (C) cyclohexyl carbamate isocyanate Nonafluoropentan-1-ol 0.02 g solid 5.00 g 10.0 g 36 2,2,3,3,4,4,5,5,6,6,6- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3538 (B) Undecafluorohexyl butylcarbamate 3.72 g Undecafluorohexan-1- 0.02 g liquid ol 11.3 g 37 Bis(2,2,3,3,4,4,5,5,6,6,6- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3721 (B) undecafluorohexyl)-{4- (isocyanato- Undecafluorohexan-1- 0.02 g oil [({[(2,2,3,3,4,4,5,5,6,6,6- methyl)octane (TIN) ol undecafluorohexyl)oxy]- 3.28 g 11.7 g carbonyl}amino)methyl]octane-1,8- diyl} biscarbamate 38 Bis(2,2,3,3,4,4,5,5,6,6,6- 2,4,4- 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3750 (B) undecafluorohexyl)-(2,2,4- Trimethylhexane Undecafluorohexan-1- 0.02 g oil trimethylhexane-1,6-diyl) 1,6-diisocyanate ol biscarbamate (TMDI) 11.1 g 3.88 g 39 Bis(2,2,3,3,4,4,5,5,6,6,6- 6-Diisocyanate- 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3826 (C) undecafluorohexyl) hexane-1,6- hexane (HDI) Undecafluorohexan-1- 0.02 g solid diylbiscarbamate 3.28 g ol 11.7 g 40 Bis(2,2,3,3,4,4,5,5,6,6,6- Dicyclohexylmethane 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.4084 (C) undecafluorohexyl)- diisocyanate Undecafluorohexan-1- 0.02 g solid (methanediyldicyclohexane-4,1-diyl) (Desmodur W) ol biscarbamate 4.55 g 10.4 g 41 2,2,3,3,4,4,5,5,6,6,6- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.4014 (C) Undecafluorohexyl-{[1,3,3-trimethyl- trimethyl-5- Undecafluorohexan-1- 0.02 g solid 5-({[(2,2,3,3,4,4,5,5,6,6,6-undeca- isocyanatomethyl- ol fluorohexyl)oxy]carbonyl}amino)- cyclohexane (IPDI) 10.9 g cyclohexyl]methyl} carbamate 4.05 g 42 2,2,3,3,4,4,5,5,6,6,6- n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3640 (B) Undecafluorohexyl hexylcarbamate 4.46 g Undecafluorohexan-1- 0.02 g liquid ol 10.5 g 43 Bis(2,2,3,3,4,4,5,5,6,6,6- Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3916 (C) undecafluorohexyl)-(4- diisocyanate Undecafluorohexan-1- 0.02 g solid methylcyclohexane-1,3-diyl) (H6TDI) ol biscarbamate 3.46 g 11.5 g 44 2,2,3,3,4,4,5,5,6,6,6- Isopropyl 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3706 (C) Undecafluorohexyl propan-2- isocyanate Undecafluorohexan-1- 0.02 g solid ylcarbamate 3.31 g ol 11.7 g 45 2,2,3,3,4,4,5,5,6,6,6- Cyclohexyl 2,2,3,3,4,4,5,5,6,6,6- Desmorapid Z 70° C. colourless 1.3956 (C) Undecafluorohexyl isocyanate Undecafluorohexan-1- 0.02 g solid cyclohexylcarbamate 4.41 g ol 10.6 g 46 2,2,3,3,4,4,5,5,6,6,7,7- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3627 (B) Dodecafluoroheptyl butylcarbamate 3.44 g Dodecafluoroheptan- 0.02 g liquid 1-ol 11.5 g 47 Bis(2,2,3,3,4,4,5,5,6,6,7,7- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3807 (B) dodecafluoroheptyl)-{4- (isocyanato- Dodecafluoroheptan- 0.02 g liquid [({[(2,2,3,3,4,4,5,5,6,6,7,7- methyl)octane (TIN) 1-ol dodecafluoroheptyl)- 3.03 g 11.9 g oxy]carbonyl}amino)methyl]octane- 1,8-diyl} biscarbamate 48 Bis(2,2,3,3,4,4,5,5,6,6,7,7- 2,4,4- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3839 (B) dodecafluoroheptyl)-(2,2,4- Trimethylhexane Dodecafluoroheptan- 0.02 g oil trimethylhexane-1,6-diyl) 1,6-diisocyanate 1-ol biscarbamate (TMDI) 11.4 g 3.60 g 49 Bis(2,2,3,3,4,4,5,5,6,6,7,7- 6-Diisocyanato- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3944 (C) dodecafluoroheptyl) hexane-1,6- hexane (HDI) Dodecafluoroheptan- 0.02 g solid diylbiscarbamate 3.03 g 1-ol 11.9 g 50 Bis(2,2,3,3,4,4,5,5,6,6,7,7- Dicyclohexyl- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4160 (A) dodecafluoroheptyl) methane Dodecafluoroheptan- 0.02 g solid (methanediyldicyclohexane-4,1-diyl) diisocyanate 1-ol biscarbamate (Desmodur W) 10.8 g 4.24 g 51 2,2,3,3,4,4,5,5,6,6,7,7- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4080 (A) Dodecafluoroheptyl-{3- trimethyl-5- Dodecafluoroheptan- 0.02 g liquid [({[(2,2,3,3,4,4,5,5,6,6,7,7- isocyanatomethyl- 1-ol dodecafluoroheptyl)oxy]carbonyl}- cyclohexane (IPDI) 11.2 g amino)methyl]-3,5,5- 3.75 g trimethylcyclohexyl}carbamate 52 2,2,3,3,4,4,5,5,6,6,7,7- n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3716 (B) Dodecafluoroheptyl hexylcarbamate 4.15 g Dodecafluoroheptan- 0.02 g liquid 1-ol 10.8 g 53 Bis(2,2,3,3,4,4,5,5,6,6,7,7- Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4020 (A) dodecafluoroheptyl)-(4- diisocyanate Dodecafluoroheptan- 0.02 g solid methylcyclohexane-1,3-diyl) (H6TDI) 1-ol biscarbamate 3.20 g 11.8 g 54 2,2,3,3,4,4,5,5,6,6,7,7- Isopropyl 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3563 (B) Dodecafluoroheptyl propan-2- isocyanate Dodecafluoroheptan- 0.02 g liquid ylcarbamate 3.06 g 1-ol 11.93 g 55 2,2,3,3,4,4,5,5,6,6,7,7- Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.3830 (B) Dodecafluoroheptyl isocyanate Dodecafluoroheptan- 0.02 g liquid cyclohexylcarbamate 4.10 g 1-ol 10.9 g 56 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3488 (B) Pentadecafluorooctyl butylcarbamate 2.97 g 8,8,8-Pentadeca- 0.02 g liquid fluorooctan-1-ol 12.0 g 57 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. pentadecafluorooctyl)-{4- (isocyanato- 8,8,8-Pentadeca- 0.02 g oil [({[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- methyl)octane (TIN) fluorooctan-1-ol pentadecafluorooctyl)oxy]carbonyl}- 2.60 g 12.4 g amino)methyl]octane-1,8-diyl} biscarbamate 58 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 2,4,4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3798 (B) pentadecafluorooctyl)-(2,2,4- Trimethylhexane 8,8,8-Pentadeca- 0.02 g oil trimethylhexane-1,6-diyl) 1,6-diisocyanate fluorooctan-1-ol biscarbamate (TMDI) 11.9 g 3.12 g 59 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 6-Diisocyanato- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. pentadecafluorooctyl) hexane-1,6- hexane (HDI) 8,8,8-Pentadeca- 0.02 g solid diylbiscarbamate 2.60 g fluorooctan-1-ol 12.4 g 60 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Dicyclohexyl- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. pentadecafluorooctyl) methane 8,8,8-Pentadeca- 0.02 g solid (methanediyldicyclohexane-4,1-diyl) diisocyanate fluorooctan-1-ol biscarbamate (Desmodur W) 11.3 g 3.70 g 61 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 1-Isocyanate-3,3,5- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3747 (B) Pentadecafluorooctyl-{[1,3,3- trimethyl-5- 8,8,8-Pentadeca- 0.02 g liquid trimethyl-5-({[(2,2,3,3,4,4,5,5,6,6,7- isocyanatomethyl- fluorooctan-1-ol 7,8,8,8- cyclohexane (IPDI) 11.7 g pentadecafluorooctyl)oxy]carbonyl}- 3.25 g amino)cyclohexyl]methyl}carbamate 62 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3595 (B) Pentadecafluorooctyl hexylcarbamate 3.61 g 8,8,8-Pentadeca- 0.02 g liquid fluorooctan-1-ol 11.4 g 63 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3900 (C) pentadecafluorooctyl)-(4- diisocyanate 8,8,8-Pentadeca- 0.02 g solid methylcyclohexane-1,3-diyl) (H6TDI) fluorooctan-1-ol biscarbamate 2.75 g 12.2 g 64 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Isopropyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4550 (A) Pentadecafluorooctyl propan-2- isocyanate 8,8,8-Pentadeca- 0.02 g solid ylcarbamate 2.63 g fluorooctan-1-ol 12.4 g 65 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. Pentadecafluorooctyl isocyanate 8,8,8-Pentadeca- 0.02 g solid cyclohexylcarbamate 3.57 g fluorooctan-1-ol 11.4 g 66 2,2,3,4,4,4-Hexafluorobutyl n-Butyl isocyanate 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.3775 (B) butylcarbamate 5.28 g Hexafluorobutan-1-ol 0.02 g liquid 9.71 g 67 Bis(2,2,3,4,4,4-hexafluorobutyl)-[4- 1,8-Diisocyanato-4- 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4180 (A) ({[(2,2,3,4,4,4- (isocyanato- Hexafluorobutan-1-ol 0.02 g oil hexafluorobutoxy)carbonyl]- methyl)octane (TIN) 10.3 g amino}methyl)octane-1,8-diyl] 4.73 g biscarbamate 68 Bis(2,2,3,4,4,4-hexafluorobutyl)- 2,4,4- 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4250 (A) (2,2,4-trimethylhexane-1,6-diyl) Trimethylhexane Hexafluorobutan-1-ol 0.02 g oil biscarbamate 1,6-diisocyanate 9.50 g (TMDI) 5.48 g 69 Bis(2,2,3,4,4,4-hexafluorobutyl) 6-Diisocyanato- 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4760 (A) hexane-1,6-diylbiscarbamate hexane (HDI) Hexafluorobutan-1-ol 0.02 g solid 4.73 g 10.3 g 70 Bis(2,2,3,4,4,4-hexafluorobutyl) Dicyclohexyl- 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4324 (C) (methanediyldicyclohexane-4,1-diyl) methane Hexafluorobutan-1-ol 0.02 g solid biscarbamate diisocyanate 8.27 g (Desmodur W) 6.27 g 71 2,2,3,4,4,4-Hexafluorobutyl-[3- 1-Isocyanato-3,3,5- 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4300 (A) ({[(2,2,3,4,4,4- trimethyl-5- Hexafluorobutan-1-ol 0.02 g oil hexafluorobutoxy)carbonyl]amino}- isocyanatomethyl- 9.31 g methyl)-3,5,5-trimethylcyclohexyl] cyclohexane (IPDI) carbamate 5.67 g 72 2,2,3,4,4,4-Hexafluorobutyl n-Hexyl isocyanate 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.3876 (B) hexylcarbamate 6.16 g Hexafluorobutan-1-ol 0.02 g liquid 8.83 g 73 Bis(2,2,3,4,4,4-hexafluorobutyl)-(4- Hexahydrotolylene 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4350 (A) methylcyclohexane-1,3-diyl) diisocyanate Hexafluorobutan-1-ol 0.02 g solid biscarbamate (H6TDI) 10.0 g 4.96 g 74 2,2,3,4,4,4-Hexafluorobutyl propan- Isopropyl 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.3810 (A) 2-ylcarbamate isocyanate Hexafluorobutan-1-ol 0.02 g oil 4.77 g 10.2 g 75 2,2,3,4,4,4-Hexafluorobutyl Cyclohexyl 2,2,3,4,4,4- Desmorapid Z 70° C. colourless 1.4220 (A) cyclohexylcarbamate isocyanate Hexafluorobutan-1-ol 0.02 g solid 6.10 g 8.88 g 76 2,2,3,3,4,4,5,5-Octafluoropentyl n-Butyl isocyanate 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.3731 (B) butylcarbamate 4.48 g Octafluoropentan-1-ol 0.02 g liquid 10.5 g 77 Bis(2,2,3,3,4,4,5,5-octafluoropentyl)- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.4100 (A) {4-[({[(2,2,3,3,4,4,5,5- (isocyanatomethyl)- Octafluoropentan-1-ol 0.02 g oil octafluoropentyl)- oxy]carbonyl}amino)methyl]octane- octane (TIN) 11.0 g 1,8-diyl} biscarbamate 3.98 g 78 Bis(2,2,3,3,4,4,5,5-octafluoropentyl)- 2,4,4- 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.4160 (A) (2,2,4-trimethylhexane-1,6-diyl) Trimethylhexane Octafluoropentan-1-ol 0.02 g oil biscarbamate 1,6-diisocyanate 10.3 g (TMDI) 4.67 g 79 Bis(2,2,3,3,4,4,5,5-octafluoropentyl) 6-Diisocyanato- 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.4026 (C) hexane-1,6-diylbiscarbamate hexane (HDI) Octafluoropentan-1-ol 0.02 g solid 3.98 g 11.0 g 80 Bis(2,2,3,3,4,4,5,5-octafluoropentyl) Dicyclohexyl- 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.4350 (A) (methanediyldicyclohexane-4,1-diyl) methane Octafluoropentan-1-ol 0.02 g solid biscarbamate diisocyanate 9.58 g (Desmodur W) 5.41 g 81 2,2,3,3,4,4,5,5-Octafluoropentyl- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.4230 (A) {[1,3,3-trimethyl-5- trimethyl-5- Octafluoropentan-1-ol 0.02 g oil ({[(2,2,3,3,4,4,5,5- isocyanatomethyl- 10.1 g octafluoropentyl)oxy]carbonyl}- cyclohexane (IPDI) amino)cyclohexyl]methyl} carbamate 4.85 g 82 2,2,3,3,4,4,5,5-Octafluoropentyl n-Hexyl isocyanate 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.3823 (B) hexylcarbamate 5.30 g Octafluoropentan-1-ol 0.02 g liquid 9.69 g 83 Bis(2,2,3,3,4,4,5,5-octafluoropentyl) Hexahydrotolylene 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.4120 (A) (4-methylcyclohexane-1,3-diyl) diisocyanate Octafluoropentan-1-ol 0.02 g oil biscarbamate (H6TDI) 10.8 g 4.19 g 84 2,2,3,3,4,4,5,5-Octafluoropentyl Isopropyl 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.3654 (B) propan-2-ylcarbamate isocyanate Octafluoropentan-1-ol 0.02 g liquid 4.02 g 10.9 g 85 2,2,3,3,4,4,5,5-Octafluoropentyl Cyclohexyl 2,2,3,3,4,4,5,5- Desmorapid Z 70° C. colourless 1.3977 (B) cyclohexylcarbamate isocyanate Octafluoropentan-1-ol 0.02 g liquid 5.25 g 9.73 g 86 2,2,3,3,4,4,5,5,6,6,7,7,7- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3507 (B) Tridecafluoroheptyl butylcarbamate 3.30 g 7- 0.02 g liquid Tridecafluoroheptan- 1-ol 11.7 g 87 Bis(2,2,3,3,4,4,5,5,6,6,7,7,7- 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3858 (C) tridecafluoroheptyl)-{4- (isocyanato- 7- 0.02 g oil [({[(2,2,3,3,4,4,5,5,6,6,7,7,7- methyl)octane (TIN) Tridecafluoroheptan- tridecafluoroheptyl)oxy]carbonyl}- 2.90 g 1-ol amino)methyl]octane-1,8-diyl} 12.1 g biscarbamate 88 Bis(2,2,3,3,4,4,5,5,6,6,7,7,7- 2,4,4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3700 (B) tridecafluoroheptyl)-(2,2,4- Trimethylhexane 7- 0.02 g oil trimethylhexane-1,6-diyl) 1,6-diisocyanate Tridecafluoroheptan- biscarbamate (TMDI) 1-ol 3.45 g 11.5 g 89 Bis(2,2,3,3,4,4,5,5,6,6,7,7,7- 6-Diisocyanato- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4002 (C) tridecafluoroheptyl) hexane-1,6- hexane (HDI) 7- 0.02 g solid diylbiscarbamate 2.90 g Tridecafluoroheptan- 1-ol 12.1 g 90 Bis(2,2,3,3,4,4,5,5,6,6,7,7,7- Dicyclohexyl- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3976 (C) tridecafluoroheptyl) (methane- methane 7- 0.02 g solid diyldicyclohexane-4,1-diyl) diisocyanate Tridecafluoroheptan- biscarbamate (Desmodur W) 1-ol 4.08 g 10.9 g 91 2,2,3,3,4,4,5,5,6,6,7,7,7- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3894 (C) Tridecafluoroheptyl-{[1,3,3- trimethyl-5- 7- 0.02 g solid trimethyl-5- isocyanatomethyl- Tridecafluoroheptan- ({[(2,2,3,3,4,4,5,5,6,6,7,7,7- cyclohexane (IPDI) 1-ol tridecafluoroheptyl)oxy]carbonyl}- 3.60 g 11.4 g amino)cyclohexyl]methyl} carbamate 92 2,2,3,3,4,4,5,5,6,6,7,7,7- n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4058 (C) Tridecafluoroheptyl hexylcarbamate 3.98 g 7- 0.02 g solid Tridecafluoroheptan- 1-ol 11.0 g 93 Bis(2,2,3,3,4,4,5,5,6,6,7,7,7- Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4002 (C) tridecafluoroheptyl)-(4- diisocyanate 7- 0.02 g solid methylcyclohexan-1,3- (H6TDI) Tridecafluoroheptan- diyl)biscarbamate 3.07 g 1-ol 11.9 g 94 2,2,3,3,4,4,5,5,6,6,7,7,7- Isopropyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3459 (B) Tridecafluoroheptyl propan-2- isocyanate 7- 0.02 g liquid ylcarbamate 2.93 g Tridecafluoroheptan- 1-ol 12.1 g 95 2,2,3,3,4,4,5,5,6,6,7,7,7- Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3856 (C) Tridecafluoroheptyl isocyanate 7- 0.02 g solid cyclohexylcarbamate 3.95 g Tridecafluoroheptan- 1-ol 11.0 g 96 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3700 (A) 11,11-Icosafluoroundecyl 2.35 g 8,8,9,9,10,10,11,11- 0.02 g solid butylcarbamate Icosafluoroundecan-1- ol 12.6 97 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3750 (A) 10,10,11,11-icosafluoroundecyl)-{4- (isocyanato- 8,8,9,9,10,10,11,11- 0.02 g solid [({[(2,2,3,3,4,4,5,5,6,6,- methyl)octane (TIN) Icosafluoroundecan-1- 7,7,8,8,9,9,10,10,11,11-icosafluoro- 2.04 g ol undecyl)oxy]carbonyl}- 12.9 g amino)methyl]octanel,8- diyl}biscarbamate 98 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 2,4,4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4000 (A) 10,10,11,11-icosafluoroundecyl)- Trimethylhexane 8,8,9,9,10,10,11,11- 0.02 g solid (2,2,4-trimethylhexane-1,6- 1,6-diisocyanate Icosafluoroundecan-1- diyl)biscarbamate (TMDI) ol 2.46 g 12.5 g 99 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 6- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 10,10,11,11-icosafluoroundecyl) Diisocyanatohexane 8,8,9,9,10,10,11,11- 0.02 g solid hexane-1,6-diylbiscarbamate (HDI) Icosafluoroundecan-1- 2.04 g ol 12.9 g 100 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, Dicyclohexylmethane 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3930 (C) 10,10,11,11-icosafluoroundecyl) diisocyanate 8,8,9,9,10,10,11,11- 0.02 g solid (methanediyldicyclohexane-4,1-diyl) (Desmodur W) Icosafluoroundecan-1- biscarbamate 2.96 g ol 12.0 g 101 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3950 (A) 11,11-Icosafluoroundecyl-{3- trimethyl-5- 8,8,9,9,10,10,11,11- 0.02 g solid [({[(2,2,3,3,4,4,5,5,6,6, isocyanatomethyl- Icosafluoroundecan-1- 7,7,8,8,9,9,10,10,11,11- cyclohexane (IPDI) ol icosafluoroundecyl)oxy]- 2.58 g 12.4 g carbonyl}amino)methyl]-3,5,5- trimethylcyclohexyl}carbamate 102 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3770 (C) 11,11-Icosafluoroundecyl 2.88 g 8,8,9,9,10,10,11,11- 0.02 g solid hexylcarbamate Icosafluoroundecan-1- ol 12.1 g 103 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3890 (C) 10,10,11,11-icosafluoroundecyl)-(4- diisocyanate 8,8,9,9,10,10,11,11- 0.02 g solid methylcyclohexan-1,3-diyl) (H6TDI) Icosafluoroundecan-1- biscarbamate 2.17 g ol 12.8 g 104 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, Isopropyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3700 (A) 11,11-Icosafluoroundecyl propan-2- isocyanate 8,8,9,9,10,10,11,11- 0.02 g solid ylcarbamate 2.06 g Icosafluoroundecan-1- ol 12.9 g 105 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 11,11-Icosafluoroundecyl isocyanate 8,8,9,9,10,10,11,11- 0.02 g solid cyclohexylcarbamate 2.85 g Icosafluoroundecan-1- ol 12.1 g 106 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3796 (C) 11,11,12,12,13,13- 2.03 g 8,8,9,9,10,10,11,11,12, 0.02 g solid Tetracosafluorotridecyl 12,13,13-Tetracosa- butylcarbamate fluorotridecan-1-ol 12.5 g 107 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 1,8-Diisocyanato-4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 10,10,11,11,12,12,13,13- (isocyanato- 8,8,9,9,10,10,11,11,12, 0.02 g solid tetracosafluorotridecyl)-{4- methyl)octane (TIN) 12,13,13-Tetracosa- [({[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 1.76 g fluorotridecan-1-ol 10,10,11,11,12,12,13,13- 13.2 g tetracosafluorotridecyl)- oxy]carbonyl}- amino)methyl]octane-1,8- diyl}biscarbamate 108 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 2,4,4- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3600 (A) 10,10,11,11,12,12,13,13- Trimethylhexane 8,8,9,9,10,10,11,11,12, 0.02 g solid tetracosafluorotridecyl)-(2,2,4- 1,6-diisocyanate 12,13,13-Tetracosa- trimethylhexane-1,6- (TMDI) fluorotridecan-1-ol diyl)biscarbamate 2.13 g 12.8 g 109 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 6- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 10,10,11,11,12,12,13,13- Diisocyanatohexane 8,8,9,9,10,10,11,11,12, 0.02 g solid tetracosafluorotridecyl) hexane-1,6- (HDI) 12,13,13-Tetracosa- diylbiscarbamate 1.76 g fluorotridecan-1-ol 13.2 g 110 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, Dicyclohexyl- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 10,10,11,11,12,12,13,13- methane 8,8,9,9,10,10,11,11,12, 0.02 g solid tetracosafluorotridecyl) diisocyanate 12,13,13-Tetracosa- (methanediyldicyclohexan-4,1- (Desmodur W) fluorotridecan-1-ol diyl)biscarbamate 2.57 g 12.4 g 111 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3934 (C) 11,11,12,12,13,13- trimethyl-5- 8,8,9,9,10,10,11,11,12, 0.02 g solid Tetracosafluorotridecyl-{[1,3,3- isocyanatomethyl- 12,13,13-Tetracosa- trimethyl-5- cyclohexane (IPDI) fluorotridecan-1-ol ({[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, 2.24 g 12.8 g 10,10,11,11,12,12,13,13- tetracosafluorotridecyl)- oxy]carbonyl}- amino)cyclohexyl]methyl}carbamate 112 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3742 (C) 11,11,12,12,13,13- 2.51 g 8,8,9,9,10,10,11,11,12, 0.02 g solid Tetracosafluorotridecyl 12,13,13-Tetracosa- hexylcarbamate fluorotridecan-1-ol 12.5 g 113 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9, Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 10,10,11,11,12,12,13,13- diisocyanate 8,8,9,9,10,10,11,11,12, 0.02 g solid tetracosafluorotridecyl)-(4- (H6TDI) 12,13,13-Tetracosa- methylcyclohexane-1,3- 1.86 g fluorotridecan-1-ol diyl)biscarbamate 13.1 g 114 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, Isopropyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3716 (C) 11,11,12,12,13,13- isocyanate 8,8,9,9,10,10,11,11,12, 0.02 g solid Tetracosafluorotridecyl propane-2- 1.78 g 12,13,13-Tetracosa- ylcarbamate fluorotridecan-1-ol 13.2 g 115 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10, Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. 11,11,12,12,13,13- isocyanate 8,8,9,9,10,10,11,11,12, 0.02 g solid Tetracosafluorotridecyl 2.48 g 12,13,13-Tetracosa- cyclohexylcarbamate fluorotridecan-1-ol 12.5 g 116 Bis(2,2,3,3-tetrafluoropropyl)-[4- 1,8-Diisocyanato-4- 2,2,3,3-Tetrafluoro-1- Desmorapid Z 70° C. colourless 1.4300 (A) ({[(2,2,3,3- (isocyanatomethyl) propanol 0.02 g oil tetrafluoropropoxy)carbonyl]amino}- octane (TIN) 9.16 g methyl)octane-1,8-diyl]biscarbamate 5.83 g 117 Bis(2,2,3,3-tetrafluoropropyl)-(2,2,4- 2,4,4- 2,2,3,3-Tetrafluoro-1- Desmorapid Z 70° C. colourless 1.4320 (A) trimethylhexane-1,6- Trimethylhexane- propanol 0.02 g liquid diyl)biscarbamate 1,6-diisocyanate 8.35 g (TMDI) 6.64 g 118 Bis(2,2,2-trifluoroethyl) hexane-1,6- 6-Diisocyanato- 1,1,1-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4178 (C) diylbiscarbamate hexane (HDI) 8.14 g 0.02 g solid 6.84 g 119 Bis(2,2,3,3-tetrafluoropropyl) 6-Diisocyanato- 2,2,3,3-Tetrafluoro-1- Desmorapid Z 70° C. colourless 1.4308 (C) hexane-1,6-diylbiscarbamate hexane (HDI) propanol 0.02 g solid 5.83 g 9.16 g 120 Bis(2,2,3,3,4,4,4-heptafluorobutyl) 6-Diisocyanato- 2,2,3,3,4,4,4- Desmorapid Z 70° C. colourless n.d. hexane-1,6-diylbiscarbamate hexane (HDI) Heptafluoro-1-butanol 0.02 g solid 4.43 g 10.6 g 121 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- 6-Diisocyanato- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless n.d. hexadecafluorononyl) hexane-1,6- hexane (HDI) 8,8,9,9-Hexadeca- 0.02 g solid diylbiscarbamate 2.44 g fluorononanol 12.5 g 122 Bis(2,2,2-trifluoroethyl)- Dicyclohexyl- 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4600 (A) (methanediyldicyclohexane-4,1- methane 6.49 g 0.02 g solid diyl)biscarbamate diisocyanate (Desmodur W) 8.50 g 123 Bis(1,1,1,3,3,3-hexafluoropropan-2- Dicyclohexyl- 1,1,1,3,3,3-Hexa- Desmorapid Z 70° C. colourless 1.4300 (A) yl) (methanediyldicyclohexane-4,1- methane fluoropropan-2-ol 0.02 g solid diyl)biscarbamate diisocyanate 8.42 g (Desmodur W) 6.57 g 124 Bis(2,2,3,3-tetrafluoropropyl)- Dicyclohexyl- 2,2,3,3-Tetra- Desmorapid Z 70° C. colourless 1.4500 (A) (methanediyldicyclohexane-4,1- methane fluoropropan-1-ol 0.02 g solid diyl)biscarbamate diisocyanate 7.52 g (Desmodur W) 7.46 g 125 Bis(2,2,3,3,4,4,4-heptafluorobutyl)- Dicyclohexyl- 2,2,3,3,4,4,4-Hepta- Desmorapid Z 70° C. colourless 1.4312 (C) (methanediyldicyclohexane-4,1- methane fluorobutan-1-ol 0.02 g solid diyl)biscarbamate diisocyanate 9.05 g (Desmodur W) 5.93 g 126 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Dicyclohexyl- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4100 (A) hexadecafluorononyl)- methane 8,8,9,9-Hexadeca- 0.02 g solid (methanediyldicyclohexane-4,1- diisocyanate fluorononan-1-ol diyl)biscarbamate (Desmodur W) 11.5 g 3.48 g 127 2,2,2-Trifluoroethyl-[(1,3,3- 1-Isocyanato-3,3,5- 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4400 (A) trimethyl-5-{[(2,2,2- trimethyl-5- 7.10 g 0.02 g oil trifluoroethoxy)carbonyl]amino}- isocyanatomethyl- cyclohexyl)methyl]carbamate cyclohexane (IPDI) 7.88 g 128 1,1,1,3,3,3-Hexafluoropropan-2-yl- 1-Isocyanato-3,3,5- 1,1,1,3,3,3-Hexa- Desmorapid Z 70° C. colourless 1.4100 (A) {3-[({[(1,1,1,3,3,3-hexafluoropropan- trimethyl-5- fluoropropan-2-ol 0.02 g solid 2-yl)oxy]carbonyl}amino)methyl]- isocyanatomethyl- 9.02 g 3,5,5-trimethylcyclohexyl}carbamate cyclohexane (IPDI) 5.96 g 129 2,2,3,3-Tetrafluoropropyl-[(1,3,3- 1-Isocyanato-3,3,5- 2,2,3,3-Tetra- Desmorapid Z 70° C. colourless 1.4394 (C) trimethyl-5-{[(2,2,3,3- trimethyl-5- fluoropropan-1-ol 0.02 g oil tetrafluoropropoxy)carbonyl]amino}- isocyanatomethyl- 8.13 g cyclohexyl)methyl]carbamate cyclohexane (IPDI) 6.85 g 130 2,2,3,3,4,4,4-Heptafluorobutyl-[3- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,4-Hepta- Desmorapid Z 70° C. colourless 1.4092 (C) ({[(2,2,3,3,4,4,4- trimethyl-5- fluorobutan-1-ol 0.02 g solid heptafluorobutoxy)carbonyl]amino}- isocyanatomethyl- 9.63 g methyl)-3,5,5- cyclohexane (IPDI) trimethylcyclohexyl]carbamate 5.35 g 131 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- 1-Isocyanato-3,3,5- 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4050 (A) Hexadecafluorononyl-{3- trimethyl-5- 8,8,9,9-Hexadeca- 0.02 g solid [({[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- isocyanatomethyl- fluorononan-1-ol hexadecafluorononyl)oxy]carbonyl}- cyclohexane (IPDI) 11.9 g amino)methyl]-3,5,5- 3.06 g trimethylcyclohexyl}carbamate 132 2,2,3,3,4,4,4-Heptafluorobutyl- n-Hexyl isocyanate 2,2,3,3,4,4,4-Hepta- Desmorapid Z 70° C. colourless 1.3745 (B) hexylcarbamate 5.82 g fluorobutan-1-ol 0.02 g liquid 9.16 g 133 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.4030 (A) Hexadecafluorononyl hexylcarbamate 3.40 g 8,8,9,9-Hexadeca- 0.02 g solid fluorononan-1-ol 11.6 g 134 Bis(2,2,2-trifluoroethyl)-(4- Hexahydrotolylene 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4334 (C) methylcyclohexane-1,3- diisocyanate 7.88 g 0.02 g solid diyl)biscarbamate (H6TDI) 7.10 g 135 Bis(1,1,1,3,3,3-hexafluoropropan-2- Hexahydrotolylene 1,1,1,3,3,3-Hexa- Desmorapid Z 70° C. colourless 1.4032 (C) yl)-(4-methylcyclohexane-1,3- diisocyanate fluoropropan-2-ol 0.02 g solid diyl)biscarbamate (H6TDI) 9.76 g 5.23 g 136 Bis(2,2,3,3-tetrafluoropropyl)-(4- Hexahydrotolylene 2,2,3,3-Tetra- Desmorapid Z 70° C. colourless 1.4340 (C) methylcyclohexane-1,3- diisocyanate fluoropropan-1-ol 0.02 g solid diyl)biscarbamate (H6TDI) 8.90 g 6.08 g 137 Bis(2,2,3,3,4,4,4-heptafluorobutyl)- Hexahydrotolylene 2,2,3,3,4,4,4-Hepta- Desmorapid Z 70° C. colourless 1.4022 (C) (4-methylcyclohexane-1,3- diisocyanate fluorobutan-1-ol 0.02 g solid diyl)biscarbamate (H6TDI) 11.3 g 4.65 g 138 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Hexahydrotolylene 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3878 (C) hexadecafluorononyl)-(4- diisocyanate 8,8,9,9-Hexadeca- 0.02 g solid methylcyclohexane-1,3- (H6TDI) fluorononan-1-ol diyl)biscarbamate 2.58 g 12.4 g 139 1,1,1,3,3,3-Hexafluoropropan-2-yl Isopropylisocyanate 1,1,1,3,3,3-Hexa- Desmorapid Z 70° C. yellow solid 1.3542 (C) propan-2-ylcarbamate 5.04 g fluoropropan-2-ol 0.02 g 9.94 g 140 2,2,3,3-Tetrafluoropropyl propan-2- Isopropylisocyanate 2,2,3,3-Tetra- Desmorapid Z 70° C. colourless 1.3831 (B) ylcarbamate 5.87 g fluoropropan-1-ol 0.02 g liquid 9.11 g 141 2,2,3,3,4,4,4-Heptafluorobutyl Isopropylisocyanate 2,2,3,3,4,4,4-Hepta- Desmorapid Z 70° C. colourless 1.3526 (B) propan-2-ylcarbamate 4.47 g fluorobutan-1-ol 0.02 g liquid 10.5 g 142 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Isopropylisocyanate 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3600 (A) Hexadecafluorononyl propan-2- 2.48 g 8,8,9,9-Hexadeca- 0.02 g oil ylcarbamate fluorononan-1-ol 12.5 g 143 2,2,2-Trifluoroethyl Cyclohexyliso- 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4256 (C) cyclohexylcarbamate cyanate 6.65 g 0.02 g solid 8.33 g 144 1,1,1,3,3,3-Hexafluoropropan-2-yl Cyclohexyliso- 1,1,1,3,3,3-Hexa- Desmorapid Z 70° C. colourless 1.4020 (C) cyclohexylcarbamate cyanate fluoropropan-2-ol 0.02 g solid 6.40 g 8.58 g 145 2,2,3,3-Tetrafluoropropyl Cyclohexyl 2,2,3,3-Tetra- Desmorapid Z 70° C. colourless 1.4296 (C) cyclohexylcarbamate isocyanate fluoropropan-1-ol 0.02 g solid 7.29 g 7.69 g 146 2,2,3,3,4,4,4-Heptafluorobutyl Cyclohexyl 2,2,3,3,4,4,4-Hepta- Desmorapid Z 70° C. colourless n.d. cyclohexylcarbamate isocyanate fluorobutan-1-ol 0.02 g solid 5.77 g 9.21 g 147 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9- Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7, Desmorapid Z 70° C. colourless 1.3930 (A) Hexadecafluorononyl isocyanate 8,8,9,9-Hexadeca- 0.02 g solid cyclohexylcarbamate 3.37 g fluorononan-1-ol 11.6 g 148 2,2,3,3,4,4,5,5,6,6,7,7- n-Butyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 60° C. colourless n.d. Dodecafluorooctane-1,8-diyl- 7.07 g Dodecafluorooctane- 0.01 g solid bis(butylcarbamate) 1,8-diol 10.9 g 149 2,2,3,3,4,4,5,5,6,6,7,7- n-Hexyl isocyanate 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4000 (A) Dodecafluorooctane-1,8-diyl- 6.18 g Dodecafluorooctane- 0.02 g solid bis(hexylcarbamate) 1,8-diol 8.80 g 150 2,2,3,3,4,4,5,5,6,6,7,7- Isopropyl 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4000 (A) Dodecafluorooctane-1,8-diyl- isocyanate Dodecafluorooctane- 0.02 g solid bis(propan-2-ylcarbamate) 4.79 g 1,8-diol 10.2 g 151 2,2,3,3,4,4,5,5,6,6,7,7- Cyclohexyl 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless n.d. Dodecafluorooctane-1,8-diyl-bis[(1- isocyanate Dodecafluorooctane- 0.02 g solid methylcyclohexyl)carbamate] 6.13 g 1,8-diol 8.85 g 152 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11, n-Butyl isocyanate 4,4,5,5,6,6,7,7,8,8,9,9, Desmorapid Z 70° C. colourless 1.4038 (C) 11-Heptadecafluoroundecane- 4.28 g 10,10,11,11,11-Hepta- 0.02 g solid 1,2-diyl-bis(butylcarbamate) decafluoro-1,2- undecanediol 10.7 g 153 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11, n-Hexyl isocyanate 4,4,5,5,6,6,7,7,8,8,9,9, Desmorapid Z 70° C. colourless 1.3988 (C) 11-Heptadecafluoroundecane- 5.08 g 10,10,11,11,11-Hepta- 0.02 g solid 1,2-diyl-bis(hexylcarbamate) decafluoro-1,2- undecanediol 9.90 g 154 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11, Isopropyl 4,4,5,5,6,6,7,7,8,8,9,9, Desmorapid Z 70° C. colourless n.d. 11-Heptadecafluoroundecane- isocyanate 10,10,11,11,11-Hepta- 0.02 g solid 1,2-diyl-bis(propan-2-ylcarbamate) 3.84 g decafluoro-1,2- undecanediol 11.1 g 155 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11, Cyclohexyl 4,4,5,5,6,6,7,7,8,8,9,9, Desmorapid Z 70° C. colourless n.d. 11-Heptadecafluoroundecane- isocyanate 10,10,11,11,11- 0.02 g solid 1,2-diyl-bis(cyclohexylcarbamate) 5.04 g Heptadecafluoro- 1,2-undecanediol 9.94 g 156 2,2,3,3,4,4,5,5-Octafluorohexane-1,6- n-Butyl isocyanate 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70° C. colourless 1.4226 (C) diyl-bis(butylcarbamate) 6.44 g fluorohexane-1,6-diol 0.02 g solid 8.54 g 157 2,2,3,3,4,4,5,5-Octafluorohexane-1,6- n-Hexyl isocyanate 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70° C. colourless n.d. diyl-bis(hexylcarbamate) 7.38 g fluorohexane-1,6-diol 0.02 g solid 7.60 g 158 2,2,3,3,4,4,5,5-Octafluorohexane-1,6- Isopropyl 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70° C. colourless n.d. diyl-bis(propan-2-ylcarbamate) isocyanate fluorohexane-1,6-diol 0.02 g solid 5.90 g 9.08 g 159 2,2,3,3,4,4,5,5-Octafluorohexane-1,6- Cyclohexyl 2,2,3,3,4,4,5,5-Octa- Desmorapid Z 70° C. colourless n.d. diyl-bis(cyclohexylcarbamate) isocyanate fluorohexane-1,6-diol 0.02 g solid 7.32 g 7.66 g 160 n-Butylcarbamate of Fluorlink E n-Butyl isocyanate Fluorlink E 10/H Desmorapid Z 70° C. colourless 1.3469 (B) 10/H 1.86 g 13.1 g 0.02 g liquid 161 n-Hexylcarbamate of Fluorlink E n-Hexyl isocyanate Fluorlink E 10/H Desmorapid Z 70° C. colourless 1.3530 (B) 10/H 2.30 g 12.7 g 0.02 g liquid 162 Isopropylcarbamate of Fluorlink E Isopropyl Fluorlink E 10/H Desmorapid Z 70° C. colourless 1.3450 (A) 10/H isocyanate 13.4 g 0.02 g liquid 1.62 g 163 Cyclohexylcarbamate of Fluorlink E Cyclohexyl Fluorlink E 10/H Desmorapid Z 70° C. colourless n.d. 10/H isocyanate 12.7 g 0.02 g liquid 2.27 g 164 1,1,1,3,3,3-Hexafluoropropan-2-yl- n-Butylisocyanate 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless 1.3912 (B) butylcarbamate 6.96 g 2-ol 0.02 g liquid 8.02 g 165 Bis(1,1,1,3,3,3-hexafluoropropan-2- 1,8-Diisocyanato-4- 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless 1.4322 (C) yl)-{4-[({[(1,1,1,3,3,3- (isocyanatomethyl) 2-ol 0.02 g oil hexafluoropropan-2-yl)oxy]- octane (TIN) 8.62 g carbonyl}amino)methyl]octane-1,8- 6.36 g diyl}biscarbamate 166 Bis(1,1,1,3,3,3-hexafluoropropan-2- 2,4,4- 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless 1.4262 (B) yl)-(2,2,4-trimethylhexan-1,6- Trimethylhexane- 2-ol 0.02 g oil diyl)biscarbamate 1,6-diisocyanate 7.80 g (TMDI) 7.18 g 167 Bis(1,1,1,3,3,3-hexafluoropropan-2- 6- 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless n.d. yl) hexane-1,6-diylbiscarbamate Diisocyanatohexane 2-ol 0.02 g solid (HDI) 8.62 g 6.36 g 168 Bis(1,1,1,3,3,3-hexafluoropropan-2- Dicyclohexylmethane 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless n.d. yl) (methanediyldicyclohexane-4,1- diisocyanate 2-ol 0.02 g solid diyl)biscarbamate (Desmodur W) 6.97 g 8.01 g 169 1,1,1,3,3,3-Hexafluoropropan-2-yl- 1-Isocyanato-3,3,5- 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless 1.4360 (C) {3-[({[(1,1,1,3,3,3-hexafluoropropan- trimethyl-5- 2-ol 0.02 g oil 2-yl)oxy]carbonyl}amino)methyl]- isocyanatomethyl- 7.59 g 3,5,5-trimethylcyclohexyl}carbamate cyclohexane (IPDI) 7.39 g 170 1,1,1,3,3,3-Hexafluoropropan-2-yl n-Hexyl isocyanate 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless 1.3996 (B) hexylcarbamate 7.90 g 2-ol 0.02 g liquid 7.08 g 171 Bis(1,1,1,3,3,3-hexafluoropropan-2- Hexahydrotolylene 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless n.d. yl)-(4-methylcyclohexane-1,3- diisocyanate 2-ol 0.02 g solid diyl)biscarbamate (H6TDI) 8.36 g 6.62 g 172 1,1,1,3,3,3-Hexafluoropropan-2-yl Isopropyl 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless 1.3870 (C) propan-2-ylcarbamate isocyanate 2-ol 0.02 g solid 6.40 g 8.58 g 173 1,1,1,3,3,3-Hexafluoropropan-2-yl Cyclohexyl 1,1,1-Trifluoropropan- Desmorapid Z 70° C. colourless n.d. cyclohexylcarbamate isocyanate 2-ol 0.02 g solid 7.84 g 7.14 g 174 2-Ethylhexyl-2,2,2-trifluoroethyl- Desmodur LD 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4940 (A) hexane-1,6-diylbiscarbamate 11.6 g 3.35 g 0.02 g solid 175 alpha-(6-{[(2,2,2- Desmodur N3400 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4450 (A) Trifluoroethoxy)carbonyl]- 9.86 g 5.12 g 0.02 g solid amino}hexyl)-omega-{[(2,2,2- trifluoroethoxy)- carbonyl]amino}poly[(2,4-dioxo-1,3- diazetidine-1,3-diyl)hexane-1,6-diyl] 176 alpha-(6-{[(2,2,2- Desmodur N3600 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4584 (C) Trifluoroethoxy)carbonyl]amino}- 9.68 g 5.30 g 0.02 g solid hexyl)-omega-[2,4,6-trioxo-3,5-bis(6- {[(2,2,2-trifluoroethoxy)carbonyl]- amino}hexyl)-1,3,5-triazinan-1- yl]poly{[2,4,6-trioxo-5-(6-{[(2,2,2- trifluoroethoxy)carbonyl]amino}- hexyl)-1,3,5-triazinane-1,3- diyl]hexane-1,6-diyl} 177 alpha-(6-{[(2,2,2- Desmodur N3900 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4200 (A) Trifluoroethoxy)carbonyl]amino}- 9.64 g 5.34 g 0.02 g solid hexyl)-omega-{[(2,2,2-trifluoro- ethoxy)carbonyl]amino}poly({(6Z)- 2,4-dioxo-6-[(6-{[(2,2,2- trifluoroethoxy)carbonyl]amino}- hexyl)imino]-1,3,5-oxadiazinane-3,5- diyl}hexane-1,6-diyl) 178 alpha-(6-{[(2,2,2-Trifluoroethoxy)- Baymicron OXA 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4562 (C) carbonyl]amino}hexyl)-omega- 10.1 g 4.90 g 0.02 g solid {[(2,2,2-trifluoroethoxy)- carbonyl]amino}poly[(2,4,6-trioxo- 1,3,5-oxadiazinane-3,5-diyl)hexane- 1,6-diyl] 179 Bis(2,2,2-trifluoroethyl)(cyclohexane- 1,3-Bis- 2,2,2-Trifluoroethanol Desmorapid Z 70° C. colourless 1.4348 (C) 1,3-diyldimethanediyl)biscarbamate (isocyanatomethyl) 7.60 g 0.02 g solid cyclohexane 7.38 g 180 2-Ethylhexyl hexafluoropropan-2-yl Desmodur LD Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4250 (A) hexane-1,6-diylbiscarbamate 10.1 g 4.88 g 0.02 g solid 181 alpha-(6-{[(Hexafluoropropan-2- Desmodur N3400 Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4400 (A) yl)carbonyl]amino}hexyl)-omega- 8.00 g 6.98 g 0.02 g solid {[(hexafluoropropan-2-yl)- carbonyl]amino}poly[(2,4-dioxo-1,3- diazetidine-1,3-diyl)hexane-1,6-diyl] 182 alpha-(6-{[(Hexafluoropropan-2- Desmodur N3600 Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4400 (A) yl)carbonyl]amino}hexyl)-omega- 7.80 g 7.18 g 0.02 g solid [2,4,6-trioxo-3,5-bis(6- {[(hexafluoropropan-2-yl)- carbonyl]amino}hexyl)-1,3,5- triazinan-1-yl]poly{[2,4,6- trioxo-5-(6-{[(hexafluoropropan-2- yl)carbonyl]amino}hexyl)-1,3,5- triazinane-1,3-diyl]hexane-1,6-diyl} 183 alpha-(6-{[(Hexafluoropropan-2- Desmodur N3900 Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4400 (A) yl)carbonyl]amino}hexyl)-omega- 7.76 g 7.22 g 0.02 g solid {[(hexafluoropropan-2-yl)- carbonyl]amino}poly({(6Z)-2,4- dioxo-6-[(6-{[(hexafluoropropan-2- yl)carbonyl]amino}hexyl)imino]- 1,3,5-oxadiazinane-3,5-diyl}hexane- 1,6-diyl) 184 alpha-(6-{[(Hexafluoropropan-2-yl)- Baymicron OXA Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4400 (A) carbonyl]amino}hexyl)-omega- 8.25 g 6.73 g 0.02 g solid {[(hexafluoropropan-2-yl)- carbonyl]amino}poly[(2,4,6-trioxo- 1,3,5-oxadiazinane-3,5-diyl)hexane- 1,6-diyl] 185 Bis(1,1,1,3,3,3-hexafluoropropan-2- 1,3-Bis- Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4100 (A) yl) (cyclohexane-1,3- (isocyanatomethyl)- 9.49 g 0.02 g solid diyldimethanediyl)biscarbamate cyclohexane 5.49 g 186 2-Ethylhexyl-2,2,3,3- Desmodur LD Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4468 (B) tetrafluoropropylhexane-1,6- 10.9 g 4.12 g 0.02 g solid diylbiscarbamate 187 alpha-(6-{[(2,2,3,3- Desmodur N3400 Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4544 (C) Tetrafluoropropyl)carbonyl]- 8.89 g 6.09 g 0.02 g solid amino}hexyl)-omega-{[(2,2,3,3- tetrafluoropropyl)- carbonyl]amino}poly[(2,4-dioxo-1,3- diazetidine-1,3-diyl)hexane-1,6-diyl] 188 alpha-(6-{[(2,2,3,3- Desmodur N3600 Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4580 (C) Tetrafluoropropyl)carbonyl]amino}- 8.70 g 6.28 g 0.02 g solid hexyl)-omega-[2,4,6-trioxo-3,5-bis(6- {[(2,2,3,3- tetrafluoropropyl)carbonyl]amino}- hexyl)-1,3,5-triazinan-1- yl]poly{[2,4,6-trioxo-5-(6-{[(2,2,3,3- tetrafluoropropyl)carbonyl]amino}- hexyl)-1,3,5-triazinane-1,3- diyl]hexane-1,6-diyl} 189 alpha-(6-{[(2,2,3,3- Desmodur N3900 Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4588 (C) Tetrafluoropropyl)carbonyl]amino}- 8.65 g 6.33 g 0.02 g solid hexyl)-omega-{[(2,2,3,3- tetrafluoropropyl)- carbonyl]amino}poly({(6Z)-2,4- dioxo-6-[(6-{[(2,2,3,3- tetrafluoropropyl)carbonyl]amino}- hexyl)imino]-1,3,5-oxadiazinane-3,5- diyl}hexane-1,6-diyl) 190 alpha-(6-{[(2,2,3,3- Baymicron OXA Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4590 (C) Tetrafluoropropyl)carbonyl]- 9.13 g 5.85 g 0.02 g solid amino}hexyl)-omega-{[(2,2,3,3- tetrafluoropropyl)- carbonyl]amino}poly[(2,4,6-trioxo- 1,3,5-oxadiazinane-3,5-diyl)hexane- 1,6-diyl] 191 Bis(2,2,3,3-Tetrafluoropropyl)- 1,3-Bis- Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4300 (A) (cyclohexane-1,3- (isocyanatomethyl)- 8.63 g 0.02 g solid diyldimethanediyl)biscarbamate cyclohexane 6.35 g 192 2-Ethylhexyl-2,2,3,3,4,4,5,5,5- Desmodur LD 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4200 (A) nonafluoropentylhexane-1,6- 8.71 g Nonafluoropentan-1-ol 0.02 g solid diylbiscarbamate 6.27 g 193 alpha-(6-{[(2,2,3,3,4,4,5,5,5- Desmodur N3400 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4200 (A) nonafluoropentan-1-oxy)carbonyl]- 6.52 g Nonafluoropentan-1-ol 0.02 g solid amino}hexyl)-omega- 8.46 g {[(2,2,3,3,4,4,5,5,5- nonafluoropentan-1- oxy)carbonyl]amino}poly[(2,4- dioxo-1,3-diazetidine-1,3- diyl)hexane-1,6-diyl] 194 alpha-(6-{[(2,2,3,3,4,4,5,5,5- Desmodur N3600 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4232 (C) nonafluoropentan-1-oxy)carbonyl]- 6.32 g Nonafluoropentan-1-ol 0.02 g solid amino}hexyl)-omega-[2,4,6-trioxo- 8.66 g 3,5-bis(6-{[(2,2,3,3,4,4,5,5,5- nonafluoropentan-1-oxy)carbonyl]- amino}hexyl)-1,3,5-triazinan-1- yl]poly{[2,4,6-trioxo-5-(6- {[(2,2,3,3,4,4,5,5,5- nonafluoropentan-1- oxy)carbonyl]amino}hexyl)-1,3,5- triazinane-1,3-diyl]hexane-1,6-diyl} 195 alpha-(6-{[(2,2,3,3,4,4,5,5,5- Desmodur N3900 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4195 (B) nonafluoropentan-1-oxy)carbonyl]- 6.28 g Nonafluoropentan-1-ol 0.02 g solid amino}hexyl)-omega- 8.70 g {[(2,2,3,3,4,4,5,5,5- nonafluoropentan-1- oxy)carbonyl]amino}poly({(6Z)- 2,4-dioxo-6-[(6-{[(2,2,3,3,4,4,5,5,5- nonafluoropentan-1-oxy)carbonyl]- amino}hexyl)imino]-1,3,5- oxadiazinane-3,5-diyl}hexane-1,6- diyl) 196 alpha-(6-{[(2,2,3,3,4,4,5,5,5- Baymicron OXA 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4216 (C) nonafluoropentan-1-oxy)carbonyl]- 6.77 g Nonafluoropentan-1-ol 0.02 g solid amino}hexyl)-omega- 8.21 g {[(2,2,3,3,4,4,5,5,5- nonafluoropentan-1- oxy)carbonyl]amino}poly[(2,4,6- trioxo-1,3,5-oxadiazinane-3,5- diyl)hexane-1,6-diyl] 197 Bis(2,2,3,3,4,4,5,5,5- 1,3-Bis- 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4012 (C) nonafluoropentyl) (cyclohexane-1,3- (isocyanatomethyl) Nonafluoropentan-1-ol 0.02 g solid diyldimethanediyl)biscarbamate cyclohexane 10.8 g 4.19 g 198 2,2,3,3,4,4,5,5,6,6,7,7- Desmodur LD 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4096 (B) Dodecafluoroheptyl-2-ethylhexyl 7.66 g Dodecafluoroheptan-1- 0.02 g solid hexane-1,6-diyl biscarbamate ol 7.32 g 199 alpha-(6-{[(2,2,3,3,4,4,5,5,6,6,7,7- Desmodur N3400 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4126 (C) Dodecafluoroheptan-1-oxy)carbonyl]- 5.50 g Dodecafluoroheptan-1- 0.02 g solid amino}hexyl)-omega- ol {[(2,2,3,3,4,4,5,5,6,6,7,7- 9.48 g dodecafluoroheptan 1-oxy)- carbonyl]amino}poly[(2,4-dioxo-1,3- diazetidine-1,3-diyl)hexane-1,6-diyl] 200 alpha-(6-{[(2,2,3,3,4,4,5,5,6,6,7,7- Desmodur N3600 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.430 (A) Dodecafluoroheptan 1-oxy)carbonyl]- 5.32 g Dodecafluoroheptan-1- 0.02 g solid amino}hexyl)-omega-[2,4,6-trioxo- ol 3,5-bis(6-{[(2,2,3,3,4,4,5,5,6,6,7,7- 9.67 g dodecafluoroheptan-1- oxy)carbonyl]amino}hexyl)- 1,3,5-triazinan-1- yl]poly{[2,4,6-trioxo-5-(6- {[(2,2,3,3,4,4,5,5,6,6,7,7- dodecafluoroheptan-1- oxy)carbonyl]amino}hexyl)-1,3,5- triazinane-1,3-diyl]hexane-1,6-diyl} 201 alpha-(6-{[(2,2,3,3,4,4,5,5,6,6,7,7- Desmodur N3900 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.410 (A) Dodecafluoroheptan-1-oxy)carbonyl]- 5.27 g Dodecafluoroheptan-1- 0.02 g solid amino}hexyl)-omega- ol {[(2,2,3,3,4,4,5,5,6,6,7,7- 9.71 g dodecafluoroheptan 1-oxy)- carbonyl]amino}poly({(6Z)-2,4- dioxo-6-[(6-{[(2,2,3,3,4,4,5,5,6,6,7, 7-dodecafluoroheptan-1- oxy)carbonyl]-amino}hexyl)imino]- 1,3,5-oxadiazinane-3,5-diyl}hexane- 1,6-diyl) 202 alpha-(6-{[(2,2,3,3,4,4,5,5,6,6,7,7- Baymicron OXA 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4100 (A) Dodecafluoroheptan 1-oxy)carbonyl]- 5.73 g Dodecafluoroheptan-1- 0.02 g solid amino}hexyl)-omega- ol {[(2,2,3,3,4,4,5,5,6,6,7,7- 9.25 g dodecafluoroheptan-1-oxy)- carbonyl]amino}poly[(2,4,6-trioxo- 1,3,5-oxadiazinane-3,5-diyl)hexane- 1,6-diyl] 203 Bis(2,2,3,3,4,4,5,5,6,6,7,7- 1,3-Bis- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4020 (A) dodecafluoroheptyl) (cyclohexane- (isocyanatomethyl) Dodecafluoroheptan-1- 0.02 g solid 1,3-diyldimethanediyl)biscarbamate cyclohexane ol 3.39 g 11.6 g 204 2-Ethylhexyl- Desmodur LD 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless 1.4262 (C) 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-penta- 6.96 g 8,8-Pentadecafluoro- 0.02 g solid decafluorooctylhexane-1,6-diyl octan-1-ol biscarbamate 8.02 g 205 alpha-(6- Desmodur N3400 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless 1.4032 (C) {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 4.87 g 8,8-Pentadecafluoro- 0.02 g solid Pentadecafluorooctan-1- octan-1-ol oxy)carbonyl]amino}hexyl)-omega- 10.1 g {[(12,2,3,3,4,4,5,5,6,6,7,7,8,8,8- pentadecafluorooctan-1-oxy)- carbonyl]amino}poly[(2,4-dioxo-1,3- diazetidine-1,3-diyl)hexane-1,6-diyl] 206 alpha-(6- Desmodur N3600 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless 1.4074 (C) {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 4.70 g 8,8-Pentadecafluoro- 0.02 g solid Pentadecafluorooctan-1- octan-1-ol oxy)carbonyl]amino}hexyl)-omega- 10.3 g [2,4,6-trioxo-3,5-bis(6- {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- pentadecafluorooctan-1- oxy)carbonyl]amino}hexyl)-1,3,5- triazinan-1-yl]poly{[2,4,6-trioxo- 5-(6-{[(12,2,3,3,4,4,5,5,6,6,7,7,8,8,8- pentadecafluorooctan-1- oxy)carbonyl]amino}hexyl)-1,3,5- triazinane-1,3-diyl]hexane-1,6-diyl} 207 alpha-(6- Desmodur N3900 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless 1.4058 (C) {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 4.65 g 8,8-Pentadecafluoro- 0.02 g solid Pentadecafluorooctan-1- octan-1-ol oxy)carbonyl]amino}hexyl)-omega- 10.3 g {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- pentadecafluorooctan-1-oxy)- carbonyl]amino}poly({(6Z)-2,4- dioxo-6-[(6- {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- pentadecafluorooctan-1-oxy)- carbonyl]amino}hexyl)imino]-1,3,5- oxadiazinane-3,5-diyl}hexane-1,6- diyl) 208 alpha-(6- Baymicron OXA 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless n.d. {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 5.09 g 8,8-Pentadecafluoro- 0.02 g solid Pentadecafluorooctan-1-oxy)- octan-1-ol carbonyl]amino}hexyl)-omega- 9.89 g {[(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- pentadecafluorooctan-1-oxy)- carbonyl]amino}poly[(2,4,6-trioxo- 1,3,5-oxadiazinane-3,5-diyl)hexane- 1,6-diyl] 209 Bis(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 1,3-Bis- 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless 1.3862 (C) pentadecafluorooctyl) (cyclohexane- (isocyanatomethyl) 8,8-Pentadecafluoro- 0.02 g solid 1,3-diyldimethanediyl) biscarbamate cyclohexane octan-1-ol 2.93 g 12.1 g 210 Butyl 3,3,4,4,5,5,6,6,7,7,8,8, n-Butanol Desmorapid Z 70° C. n.d. (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- 9,9,10,10,10- 0.23 g 0.001 g heptadecafluorodecyl)carbamate Heptadecafluorodecyl isocyanate 1.52 g 211 Isopropyl 3,3,4,4,5,5,6,6,7,7,8,8, Isopropanol Desmorapid Z 70° C. n.d. (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- 9,9,10,10,10- 0.23 g 0.001 g heptadecafluorodecyl)carbamate Heptadecafluorodecyl isocyanate 1.52 g 212 1,1,1,3,3,3-Hexafluoropropan-2-yl 3,3,4,4,5,5,6,6,7,7,8,8, Hexafluoro-2-propanol Desmorapid Z 70° C. n.d. (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- 9,9,10,10,10- 0.38 g 0.001 g heptadecafluorodecyl)carbamate Heptadecafluorodecyl isocyanate 1.12 g 213 2,2,2-Trifluoroethyl phenylcarbamate Phenyl isocyanate Trifluoroethanol Desmorapid Z 60° C. colourless 1.4838 (C) 81.5 g 68.4 g 0.07 g solid 214 1,1,1,3,3,3-Hexafluoropropan-2-yl Phenyl isocyanate Hexafluoro-2-propanol Desmorapid Z 60° C. colourless 1.4476 (C) phenylcarbamate 8.29 g 11.7 g 0.01 g solid 215 1,1,1,3,3,3-Hexafluoropropan-2-yl- 2,2,2-Trifluoroethyl Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4280 (C) 2,2,2-trifluoroethylhexane-1,6-diyl (6-isocyanato- 4.75 g 0.01 g solid biscarbamate hexyl)carbamate 5.24 g 216 2,2,3,3-Tetrafluoropropyl-2,2,2- 2,2,2-Trifluoroethyl Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4514 (C) trifluoroethylhexane-1,6-diyl (6-isocyanato- 4.16 g 0.01 g solid biscarbamate hexyl)carbamate 5.83 g 217 2,2,3,3,4,4,5,5,5-Nonafluoropentyl- 2,2,2-Trifluoroethyl 2,2,3,3,4,4,5,5,5- Desmorapid Z 70° C. colourless 1.4168 (C) 2,2,2-trifluoroethylhexane-1,6-diyl (6-isocyanato- Nonafluoropentan-1-ol 0.01 g solid biscarbamate hexyl)carbamate 5.74 4.25 g 218 2,2,3,3,4,4,5,5,6,6,7,7- 2,2,2-Trifluoroethyl 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4172 (C) Dodecafluoroheptyl-2,2,2- (6-isocyanato- Dodecafluoroheptan-1- 0.01 g solid trifluoroethylhexane-1,6-diyl hexyl)carbamate ol biscarbamate 3.57 g 5.74 g 219 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- 2,2,2-Trifluoroethyl 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless n.d. Pentadecafluorooctyl-2,2,2- (6-isocyanato- 8,8-Pentadecafluoro- 0.01 g solid trifluoroethylhexane-1,6-diyl hexyl)carbamate octan-1-ol biscarbamate 3.16 g 6.83 g 220 2,2,3,3,4,4,5,5-Octafluoropentyl- 2,2,3,3,4,4,5,5- Trifluoroethanol Desmorapid Z 70° C. colourless 1.4236 (C) 2,2,2-trifluoroethylhexane-1,6-diyl Octafluoropentyl 2.31 g 0.01 g solid biscarbamate (6-isocyanato- hexyl)carbamate 7.68 g 221 1,1,1,3,3,3-Hexafluoropropan-2-yl- 2,2,3,3,4,4,5,5- Hexafluoro-2-propanol Desmorapid Z 70° C. colourless 1.4086 (C) 2,2,3,3,4,4,5,5- Octafluoropentyl 3.35 g 0.01 g oil octafluoropentylhexane-1,6-diyl (6-isocyanato- biscarbamate hexyl)carbamate 6.64 g 222 2,2,3,3,4,4,5,5-Octafluoropentyl- 2,2,3,3,4,4,5,5- Tetrafluoro-1-propanol Desmorapid Z 70° C. colourless 1.4256 (C) 2,2,3,3-tetrafluoropropylhexane-1,6- Octafluoropentyl 2.84 g 0.01 g solid diyl biscarbamate (6-isocyanato- hexyl)carbamate 7.15 g 223 2,2,3,3,4,4,5,5,6,6,7,7- 2,2,3,3,4,4,5,5- 2,2,3,3,4,4,5,5,6,6,7,7- Desmorapid Z 70° C. colourless 1.4048 (C) Dodecafluoroheptyl-2,2,3,3,4,4,5,5- Octafluoropentyl Dodecafluoroheptan-1- 0.01 g oil octafluoropentylhexane-1,6-diyl (6-isocyanato- ol biscarbamate hexyl)carbamate 4.99 g 5.00 g 224 2,2,3,3,4,4,5,5-Octafluoropentyl- 2,2,3,3,4,4,5,5- 2,2,3,3,4,4,5,5,6,6,7,7,8, Desmorapid Z 70° C. colourless 1.3970 (C) 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8- Octafluoropentyl 8,8-Pentadecafluoro- 0.01 g solid pentadecafluorooctylhexane-1,6-diyl (6-isocyanato- octan-1-ol biscarbamate hexyl)carbamate 5.45 g 4.54 g

Example 225 9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31,31,32,32, 33,33,34,34-Tetracosafluoro-20,20,22-trimethyl-6,17,26-trioxo-7,16,27-trioxa-5,18,25-triazapentatriacontan-35-yl butylcarbamate

2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-1,8-octanediol was initially introduced into a 250 ml round-bottomed flask and 0.05 g of dibutyltin dilaurate (Desmorapid Z, Bayer MaterialScience AG, Leverkusen, Germany) was added and heated to 60° C. 18.7 g of n-butyl isocyanate were added in portions and stirring was effected for 3 h at 60° C. Thereafter, 19.9 g of 2,4,4-trimethylhexane 1,6-diisocyanate (TMDI) were added dropwise and the mixture was further kept at 60° C. until the isocyanate content had fallen below 0.1%. Thereafter, cooling was effected and the product was obtained as a colourless oil; the refractive index determined according to method B is n_(D) ²⁰=1.4131.

Example 226 23-(8,8,9,9,10,10,11,11,12,12,13,13-Dodecafluoro-5,16-dioxo-6,15-dioxa-4,17-diazahenicos-1-yl)-9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31, 31,32,32,33,33,34,34-tetracosafluoro-6,17,26-trioxo-7,16,27-trioxa-5,18,25-triaza-pentatriacontan-35-yl butylcarbamate

2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-1,8-octanediol was initially introduced into a 100 ml round-bottomed flask and 0.01 g of dibutyltin dilaurate (Desmorapid Z, Bayer MaterialScience AG, Leverkusen, Germany) was added and heated to 60° C. 3.63 g of n-butyl isocyanate were added in portions and stirring was effected for 3 h at 60° C. Thereafter, 3.08 g of 1,8-diisocyanato-4-(isocyanatomethyl)octane (TIN) were added dropwise and the mixture was further kept at 60° C. until the isocyanate content had fallen below 0.1%. Thereafter, cooling was effected and the product was obtained as a colourless oil; the refractive index determined according to method A is n=1.4200.

Production of the Media

For testing the optical properties, media were produced and optically measured as described below:

Preparation of the Polyol Component

0.18 g of tin octanoate, 374.8 g of ε-caprolactone and 374.8 g of a difunctional polytetrahydrofuran polyether polyol (equivalent weight 500 g/mol OH) were initially introduced in a 1 l flask and heated to 120° C. and kept at this temperature until the solids content (proportion of non-volatile constituents) was 99.5% by weight or more. Thereafter, cooling was effected and the product was obtained as a waxy solid.

Preparation of Urethane Acrylate 1: phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate

0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate (Desmorapid Z, Bayer MaterialScience AG, Leverkusen, Germany) and 213.07 g of a 27% strength solution of tris(p-isocyanatophenyl)thiophosphate in ethyl acetate (Desmodur® RFE, product of Bayer MaterialScience AG, Leverkusen, Germany) were initially introduced into a 500 ml round-bottomed flask and heated to 60° C. Thereafter, 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was further kept at 60° C. until the isocyanate content had fallen below 0.1%. Thereafter, cooling was effected and ethyl acetate was completely removed in vacuo. The product was obtained as a semicrystalline solid.

Preparation of Urethane Acrylate 2: 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)-propyl prop-2-enoate

0.05 g of 2,6-di-tert-butyl-4-methylphenol, 0.02 g of Desmorapid Z, 26.8 g of 3-(methylthio)phenyl isocyanate in 50 g of ethyl acetate were initially introduced into a 250 ml round-bottomed flask and heated to 60° C. Thereafter, 21.1 g of 2-hydroxypropyl acrylate were added dropwise and the mixture was further kept at 60° C. until the isocyanate content had fallen below 0.1%. Thereafter, the ethyl acetate was distilled off at 5 mbar and cooling was effected. The product was obtained as a light yellow liquid.

Medium 1:

3.82 g of the polyol component prepared as described above were mixed with 2.50 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 2.50 g of 2,2,2-trifluoroethyl hexylcarbamate (Example 4), 0.10 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.01 g of new methylene blue and 0.35 g of N-ethylpyrrolidone at 60° C. so that a clear solution was obtained. Thereafter, cooling to 30° C. was effected, 0.71 g of Desmodur® N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) was added and mixing was effected again. Finally, 0.006 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and mixing was effected again briefly. The liquid material obtained was then poured on to a glass plate and covered there with a second glass plate which was kept at a distance of 20 μm by spacers. This test specimen was left to stand for 12 hours at room temperature and cured.

The media 2-13 were prepared in an analogous manner from the examples shown in Table 1. In each case, Table 2 states which example compound was present with which content in the photopolymer formulation. The Δn values determined for the photopolymer formations prepared are likewise summarized in Table 2.

Medium 14:

3.40 g of the polyol component prepared as described above were mixed with 2.00 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 2.00 g of 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)propyl prop-2-enoate (urethane acrylate 2), 1.50 g of 2,2,2-trifluoroethyl hexylcarbamate (Example 4), 0.10 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.01 g of new methylene blue and 0.35 g of N-ethylpyrrolidone at 60° C. so that a clear solution was obtained. Thereafter, cooling to 30° C. was effected, 0.64 g of N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) was added and mixing was effected again. Finally, 0.006 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and mixing was effected again briefly. The liquid material obtained was then poured on to a glass plate and covered there with a second glass plate which was kept at a distance of 20 μm by spacers. This test specimen was left to stand for 12 hours at room temperature and cured.

The media 14-70 were prepared in an analogous manner from the examples shown in Table 1. In each case, Table 3 states which example compound was present with which content in the photopolymer formulation. The Δn values determined for the photopolymer formations prepared are likewise summarized in Table 3.

Comparative Medium I:

8.89 g of the polyol component prepared as described above were mixed with 3.75 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 0.15 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.015 g of new methylene blue and 0.53 g of N-ethylpyrrolidone were mixed at 60° C. so that a clear solution was obtained. Thereafter, cooling to 30° C. was effected, 1.647 g of Desmodur® N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) were added and mixing was effected again. Finally, 0.009 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and mixing was effected again briefly. The liquid material obtained was then poured on to a glass plate and covered there with a second glass plate which was kept at a distance of 20 μm by spacers. This test specimen was left to stand for 12 hours at room temperature and cured.

Comparative Medium II:

3.82 g of the polyol component prepared as described above were mixed with 2.50 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 2.50 g of propylene carbonate (Comparative Example II), 0.10 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.010 g of new methylene blue and 0.35 g of N-ethylpyrrolidone were mixed at 60° C. so that a clear solution was obtained. Thereafter, cooling to 30° C. was effected, 0.702 g of Desmodur® N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) was added and mixing was effected again. Finally, 0.022 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and mixing was effected again briefly. The liquid material obtained was then poured on to a glass plate and covered there with a second glass plate which was kept at a distance of 20 μm by spacers. This test specimen was left to stand for 12 hours at room temperature and cured.

The comparative media III-V were prepared in an analogous manner from the comparative examples shown in Table 2.

Comparative Medium VI

4.66 g of the polyol component prepared as described above were mixed with 2.00 g of phosphorothioyltris(oxybenzene-4,1-diylcarbamoyloxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 2.00 g of 2-({[3-(methylsulphanyl)phenyl]carbamoyl}oxy)propyl prop-2-enoate (urethane acrylate 2), 0.10 g of CGI 909 (experimental product of Ciba Inc, Basle, Switzerland), 0.010 g of new methylene blue and 0.35 g of N-ethylpyrrolidone at 60° C. so that a clear solution was obtained. Thereafter, cooling to 30° C. was effected, 0.87 g of Desmodur® N3900 (commercial product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%) was added and mixing was effected again. Finally, 0.006 g of Fomrez UL 28 (urethanization catalyst, commercial product of Momentive Performance Chemicals, Wilton, Conn., USA) was added and mixing was effected again briefly. The liquid material obtained was then poured on to a glass plate and covered there with a second glass plate which was kept at a distance of 20 μm by spacers. This test specimen was left to stand for 12 hours at room temperature and cured.

TABLE 2 Holographic evaluation of selected examples in the formulation with 25% of urethane acrylate 1 and 25% of additive (fluorinated urethane). Medium Δn Example, [% by weight] 1 4, 25 0.0198 2 2, 25 0.0187 3 5, 25 0.0235 4 6, 25 0.0183 5 9, 25 0.0220 6 11, 25 0.0210 7 12, 25 0.0194 8 14, 25 0.0223 9 15, 25 0.0150 10 19, 25 0.0173 11 20, 25 0.0249 12 21, 25 0.0257 13 214, 25 0.0152 Comparative examples, [% by weight] I No additive 0.0115 II Propylene carbonate, 25 0.0136 III Dimethyl adipate, 25 0.0146 IV Diethylene glycol diacetate, 25 0.0146 V Triethyl citrate, 25 0.0115

The values described for Δn were achieved at doses of 4-32 ml/cm².

The values found for the holographic property Δn of the holographic media show that the commercial additives used in the comparative medium is less suitable for use in holographic media, whereas the urethanes according to the invention are very suitable in the media 1 to 13 for the preparation of holographic media, owing to the higher value for Δn.

TABLE 3 Holographic evaluation of selected examples in the formulation with 20% by weight of urethane acrylate 1, 20% by weight of urethane acrylate 2 and 15% by weight of additive (fluorinated urethane). Medium Δn Example, [% by weight] 14 2, 15 0.0253 15 4, 15 0.0238 16 5, 15 0.0302 17 7, 15 0.0305 18 8, 15 0.0220 19 14, 15 0.0284 20 15, 15 0.0205 21 19, 15 0.0235 22 20, 15 0.0310 23 21, 15 0.0330 24 26, 15 0.0365 25 32, 15 0.0348 26 35, 15 0.0295 27 36, 15 0.0217 28 46, 15 0.0261 29 48, 15 0.0261 30 51, 15 0.0230 31 52, 15 0.0310 32 54, 15 0.0310 33 55, 15 0.0245 34 66, 15 0.0250 35 67, 15 0.0260 36 68, 15 0.0250 37 71, 15 0.0230 38 72, 15 0.0234 39 73, 15 0.0240 40 74, 15 0.0260 41 75, 15 0.0225 42 76, 15 0.0204 43 82, 15 0.0239 44 84, 15 0.0203 45 132, 15 0.0286 46 133, 15 0.0283 47 141, 15 0.0239 48 146, 15 0.0210 49 147, 15 0.0272 50 164, 15 0.0220 51 165, 15 0.0229 52 166, 15 0.0209 53 170, 15 0.0235 54 172, 15 0.0245 55 174, 15 0.0202 56 175, 15 0.0201 57 180, 15 0.0230 58 181, 15 0.0235 59 182, 15 0.0255 60 183, 15 0.0248 61 184, 15 0.0233 62 192, 15 0.0261 63 198, 15 0.0269 64 201, 15 0.0210 65 202, 15 0.0262 66 203, 15 0.0305 67 220, 15 0.0229 68 221, 15 0.0279 69 222, 15 0.0221 70 223, 15 0.0303 Comparative example VI No additive 0.0140

The values described for Δn were achieved at doses of 4-32 mJ/cm².

The values found for the holographic property Δn of the holographic media show that fluorinated urethanes according to the invention are very suitable in the media 14 to 70 for the preparation of holographic media, owing to the high values for Δn. 

1.-15. (canceled)
 16. A photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, wherein the photopolymer formulation further comprises fluorourethanes as plasticizers.
 17. The photopolymer formulation according to claim 16, wherein the fluorourethanes have at least one structural element of the formula (I)

and are substituted by at least one fluorine atom.
 18. The photopolymer formulation according to claim 16, wherein the fluorourethanes comprise compounds having the formula (II)

wherein n is from 1 to 8 and R¹, R², R³ represent, independently of one another, hydrogen or linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms, at least one of the radicals R¹, R², R³ being substituted by at least one fluorine atom.
 19. The photopolymer formulation according to claim 18, wherein R¹ represents an organic radical having at least one fluorine atom.
 20. The photopolymer formulation according to claim 18, wherein R¹ comprises 1-20 CF₂ groups and/or one or more CF₃ groups, R² comprises a C1-C20 alkyl radical or hydrogen, and R³ comprises a C1-C20 alkyl radical or hydrogen.
 21. The photopolymer formulation according to claim 18, wherein R¹ comprises 1-10 CF₂ groups and/or one or more CF₃ groups, R² comprises a C1-C10 alkyl radical or hydrogen, and R³ comprises a C1-C₁₀ alkyl radical or hydrogen.
 22. The photopolymer formulation according to claim 18, wherein R¹ comprises 1-8 CF₂ groups and/or one or more CF₃ groups.
 23. The photopolymer formulation according to claim 16, wherein the fluorourethanes comprise uretdione, isocyanurate, biuret, allophanate, polyurea, oxadiazadione and/or iminooxadiazinedione structural elements and/or mixtures of these structural elements.
 24. The photopolymer formulation according to claim 16, wherein the fluorourethanes have a refractive index n_(D) ²⁰ of ≦1.4600.
 25. The photopolymer formulation according to claim 16, wherein the fluorourethanes have a refractive index n_(D) ²⁰ of ≦1.4300.
 26. The photopolymer formulation according to claim 16, wherein the fluorourethanes have a fluorine content of 10-80% by weight.
 27. The photopolymer formulation according to claim 16, wherein the fluorourethanes have a fluorine content of 17.5-65% by weight.
 28. The photopolymer formulation according to claim 16, wherein the matrix polymers comprise polyurethanes.
 29. The photopolymer formulation according to claim 16, wherein the writing monomers comprise acrylates.
 30. The photopolymer formulation according to claim 29, wherein the acrylates have a refractive index of n_(D) ²⁰>1.50.
 31. The photopolymer formulation according to claim 16, wherein the photopolymer formulation consists essentially of 15 to 79 by weight of matrix polymers, 5 to 50 by weight of writing monomers, 1 to 10 by weight of photoinitiators and 5 to 50 by weight of fluorourethanes and 0 to 10% by weight of further additives, wherein the sum of the constituents being 100% by weight.
 32. Holographic elements and images formed from the photopolymer formulation according to claim
 16. 33. A method for exposing holographic media comprising the photopolymer formulation according to claim 16, wherein the method comprises selectively polymerizing the writing monomers with spatial resolution by electromagnetic radiation.
 34. Fluorourethane, obtained by reacting a polyisocyanate which comprises iminooxadiazinediones or oxadiazadione and has at least one free isocyanate group with an alcohol, wherein the polyisocyanate and/or the alcohol are substituted by at least one fluorine atom.
 35. Fluorourethanes according to the formula (III)

wherein m is from 1 to 8 and R⁴, R⁵, R⁶ represent, independently of one another, hydrogen or linear, branched, cyclic or heterocyclic organic radicals which are unsubstituted or optionally also substituted by heteroatoms and have iminooxadiazinedione and/or oxadiazadione structural elements, wherein at the same time at least two of the radicals R⁴, R⁵, R⁶ are substituted by at least one fluorine atom. 